FERROELECTRIC FILM, FERROELECTRIC CAPACITOR, FERROELECTRIC MEMORY, PIEZOELECTRIC DEVICE, SEMICONDUCTOR DEVICE, METHOD FOR MANUFACTURING FERROELECTRIC FILM, AND METHOD FOR MANUFACTURING FERROELECTRIC CAPACITOR

Figure 1 shows a mimetic a ferroelectric capacitor also shown a cross section.

Also Figure 2 shows a PZTN film spin-coating for forming the electrons into flow scheme shown the surfaces of the laminated structure in.

P of ferroelectric capacitor also Figure 3 shows a (polarization)-V (voltage) hysteresis curve, which illustrates the surface.

In the embodiment 1 in the of Figure 4 A ∼of Figure 4 C PZTN drawing, which illustrates the surface of the film morphology.

The of Figure 5 A ∼of Figure 5 C crystallinity of PZTN film in the embodiment 1, as shown in drawing.

In the of Figure 6 A ∼of Figure 6 C PZTN film and a surface morphology in the embodiment 1 according to the drawing.

In the of Figure 7 A ∼of Figure 7 C PZTN film in the embodiment 1 according to the with crystalline and drawing.

In the of Figure 8 A ∼of Figure 8 C PZTN film in the embodiment 1, as shown as the gain varied amount of an and drawing.

In the of Figure 9 A ∼of Figure 9 C PZTN film in the embodiment 1, as shown as the gain varied amount of an and drawing.

In the of Figure 10 B and of Figure 10 A PZTN film in the embodiment 1, as shown provided to decrease a leakage current of drawing.

The of Figure 11 A PZTN of the film fatigue characteristics wherein in the embodiment 1, as shown in drawing, in the embodiment 1 in the of Figure 11 B PZTN drawing, which illustrates the static imprint properties of the film.

Also in the embodiment 1 in Figure 12 shows a by ozone TEOS SiO₂ formed passivation layer surface, which illustrates the structure of ferroelectric capacitor.

Also in the embodiment 1 in Figure 13 shows a by ozone TEOS SiO₂ of ferroelectric capacitor of the semiconductor layer, as shown much as the gain varied amount of surface.

Figure 14 shows a of the existing method PZT film provided to decrease a leakage current of in also in the embodiment 1, which illustrates the surface.

Also in the embodiment 1 in Figure 15 shows a of the existing method PZT film fatigue characteristics wherein of a ferroelectric capacitor, as shown surface.

Figure 16 shows a of the existing method PZT film also in the embodiment 1 in static imprint characteristics of a ferroelectric capacitor shows the surfaces of the laminated structure in.

In the embodiment 2 in the of Figure 17 B and of Figure 17 A PZTN, as shown much as the gain varied amount of drawing of the film.

In the embodiment 2 in the of Figure 18 B and of Figure 18 A PZTN, as shown much as the gain varied amount of drawing of the film.

In the embodiment 2 in the of Figure 19 B and of Figure 19 A PZTN, as shown much as the gain varied amount of drawing of the film.

Also in the embodiment 2 in Figure 20 shows a PZTN of the film X ray diffraction pattern, as shown surface.

Figure 21 shows a PZTN determined also in the embodiment 2 in a composition ratio between Pb Nb and defect in an object the surfaces of the laminated structure in.

Also Figure 22 shows a perovskite crystalline WO₃ side account for crystal structure of.

In the embodiment 3 in the of Figure 23 A ∼of Figure 23 C PZTN shown mimetic a catalyst layer forming step of forming of the film a cross-sectional drawing.

In the embodiment 3 in the of Figure 24 B and of Figure 24 A PZTN to illustrate the change of lattice constant of the film for drawing.

Also in the embodiment 3 in Figure 25 shows a lattice mismatch between a PZTN film and the total ratio Pt metal film side account for change.

Also reference in Figure 26 shows a of the existing method PZT film spin-coating for forming the electrons into the surfaces of the laminated structure in shown flow.

The reference of Figure 27 A ∼of Figure 27 E PZT in drawing, which illustrates the surface of the film morphology.

Reference in the of Figure 28 A ∼of Figure 28 E crystallinity of drawing, which illustrates the PZT film.

The reference of Figure 29 B and of Figure 29 A PZT tetragonal in drawing, which illustrates the hysteresis of the film.

PZT tetragonal of the existing method in reference also Figure 30 shows a hysteresis, which illustrates the surface of the film.

Reference in the of Figure 31 B and of Figure 31 A tetragonal PZT film of lOc type drawing, which illustrates the analysis result.

The of Figure 32 A ∼of Figure 32 C a drawing process for manufacturing ferroelectric capacitor.

The of Figure 33 B and of Figure 33 A, of drawing, as shown much as the gain varied amount of ferroelectric capacitor.

Figure 34 shows a electrical characteristics of ferroelectric capacitor also shows the surfaces of the laminated structure in.

The simple matrix the capacitors are shared ferroelectric memory device of Figure 35 A a mimetic shown a plane view, the simple matrix the capacitors are shared ferroelectric memory device of Figure 35 B a mimetic shown a cross-sectional drawing.

Figure 36 shows a memory cell array on the same substrate for with peripheral circuit is integrated onto device shown one example of a cross section.

The 1T1C-type ferroelectric memory of Figure 37 A shown mimetic a cross-sectional drawing, the 1T1C-type ferroelectric memory of Figure 37 B shown mimetic the distance is vertical to the circuit diagram.

A ferroelectric has of Figure 38 A ∼of Figure 38 C a drawing memory and manufacturing process.

Decomposition of head log Figure 39 shows a perspective view.

Plane view of the recording head of Figure 40 A, of Figure 40 B cross-sectional drawing of the recording head.

Figure 41 shows a mimetic layer structure of a piezoelectric element also shown a cross section.

Figure 42 shows a also ink jet recording device a coarse one example of it is shown a.

The PZT to of Figure 43 A Ta is added is drawing, as shown much as the gain varied amount of ferroelectric, the PZT to of Figure 43 B W is added is drawing, as shown much as the gain varied amount of ferroelectric.

Figure 44 shows a also PZT-based ferroelectric number of properties combining at an of elements constituting, as shown surface.

Of Figure 45 A ∼of Figure 45 C has lighter mirror light type Schottky crystal structure drawing to explain the deficiency.

Figure 46 shows a space charge polarization also ferroelectric to explain the surface.

(1) the present embodiment form according to 2005, AB_1-x Nb_x O₃ to represent the general formula of, A element consists at least Pb, Zr B element, Ti, V, W, Ta and Hf during, and consists for more than at least one, 0.05≤x includes Nb in a range of < 1.

Furthermore, A element Pb_1-y Ln_y (0 < y≤0.2) .can be comprised of. And, the Ln La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, during Lu and Yb, consists for more than can be at least one.

(2) the present embodiment form according to 2005, (Pb_1-y A_y) (B_1-x Nb_x) O₃ exhibits having a formula of, La A element, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and comprises at least one of Yb and Lu, B element Zr, Ti, V, W, Ta and Hf made one or more, 0.05≤x < 1 (more preferably, 0.1≤x≤0.3) includes Nb in a range of.

(3) the present embodiment form according to 2005, a large composition Ti than composition Zr, during composition in addition Ti 40mol % hereinafter 2.5mol % or more (more preferably, 30mol % hereinafter 10mol % or more) is Nb is substituted with a PZT-based ferroelectric. Furthermore, if royal tomb the body political world and tetragonal 2005 based PZT is at least one material may have a crystal structure of. Furthermore, is PZT-based 2005 0.5mol % or more (more preferably, 0.5mol % or more, less than 5mol %)of Si or Si Ge and may include a. Furthermore, is PZT-based 2005, sol-gel solution for the formation can be is formed by an.

(4) the present embodiment form according to 2005, ABO₃ with e.g. a general formula of, as elements constituting site A includes Pb, Ti and Zr B site, as elements constituting is for including PZT-based ferroelectric. Is PZT-based 2005, said amount Pb site defect A ABO₃ of a stoichiometric composition is most 20mol % hereinafter. Is 2005, the convexity on the Pb site 2 amount of defect said A significant B ratio a composition may include a Nb site. Is 2005, B higher composition Zr composition is Ti service site, if royal tomb the body political world in addition material may have a crystal structure. Furthermore, is 2005 sol-gel solution for the formation can be is formed by an.

(5) the present embodiment form ferroelectric according to the manufacturing method, manufacturing method as PZT-based ferroelectric, said sol-gel solution for the formation as, PbZrO₃ for sol-gel solution for the formation, PbTiO₃ for sol-gel solution for the formation, and PbNbO₃ mixing a sol-gel solution for the formation for use of.

Ferroelectric in manufacturing method according to the present embodiment form, as said sol-gel solution for the formation, in addition PbSiO₃ for mixing a sol-gel solution for the formation can be using.

(6) the present embodiment form ferroelectric according to the manufacturing method, manufacturing method as PZT-based ferroelectric, a elements constituting site A Pb 1 stoichiometry composition according to the above constitution, Pb is 0.9 ∼ 1.2 range of included sol-gel solution for the formation is formed by an..

(7) the present embodiment form ferroelectric according to the manufacturing method, said PZT-based ferroelectric, on a metallic platinum group metal to form a may include a.

(8) the present embodiment form according to ferroelectric in manufacturing method, the platinum group metal said, Pt Ir and can be at least any one of.

(9) the present embodiment form according to ferroelectric memory, pre Si is formed over a wafer a drain electrode or the source of the transistor CM0S either and high conduction the number 1 electrode and high walls are ferroelectric said number 1, number 2 formed on said ferroelectric electrode, said number 1 electrode, said a ferroelectric layer, and an said number 2 is a capacitor constructed by the electrode, a is formed over a wafer Si CM0S pre selected by the transistor as ferroelectric memory that performs, at least 50% Ti 2005 said ratio consists tetragonal PZT, during composition Ti and Nb is 40mol % hereinafter 5mol % or more are substituted with, simultaneously for Ge 1mol % or more Si and be at 500 including ferroelectric.

(10) the present embodiment according to ferroelectric memory form, a pre-fabricated number 1 electrode and, and in a direction transverse to current electrode said number 1 number 2 electrode and arranged, said number 2 electrode and at least said number 1 is applied to the anti-ferroelectric is located in the intersection area electrode includes, said number 1 electrode, said number 2 a ferroelectric layer, and an said capacitor configured by the electrode which are disposed in the form ferroelectric memory as a matrix, said PZT tetragonal or more 50% ratio Ti 2005 consists, during composition Ti and Nb is 40mol % hereinafter are substituted with 5mol % or more, including ferroelectric for Ge 1mol % or more Si and simultaneously be at 500.

(11) the present embodiment form power consumption of the ferroelectric memory according to the manufacturing method, a raw material liquid number 1 PbZrO₃ number 2 and sol-gel solution for the formation for forming a raw material liquid PbTiO₃ number 3 and sol-gel solution for the formation for forming a raw material liquid PbNbO₃ number 4 and sol-gel solution for the formation for forming a raw material liquid PbSiO₃ for coating sol-gel solution for the formation for forming after crystallized comprising a step, said number 1, number 2, number 3 and for forming a ferroelectric layer raw material liquid is raw material liquid containing an, number 4 the raw material liquid number 1, number 2, number 3 and a ferroelectric layer needed, to formed as having as their catalytic effect is indispensable for a for generating an 126a is raw material liquid containing an.

(12) the manufacturing method of ferroelectric capacitor according to the present embodiment form, exposed to the outside and for forming the lower electrode on, the semiconductor substrate and the bottom electrode said Pb, Zr, Ti, Nb and composite oxides as constituent elements including PZTN ferroelectric, and, said electrode material on the electrically couples each of the upper regions and, said lower electrode, ferroelectric, and an upper electrode so as to cover the and a polyvinyl alcohol film in which a, the semiconductor layer after at least said, for said PZTN of crystallizing the composite oxide as to applying the heat treatment.

According to the present embodiment, as material ferroelectric Pb, Zr, Ti, and Nb as constituent elements using composite oxide including PZTN, such PZTN composite oxide crystallization. carried out after the capable of forming a protection film. To this end, e.g. for forming protective film upon an insulation with hydrogen generated during the process damage the obtained policy is receiving, for crystallisation then by being thermal treatment is performed, this damage while regaining PZTN. is crystallized composite oxide. Therefore, upper and side surfaces with, ferroelectric reduction reaction for protecting against method of forming barrier film collector, a process, an improvement in productivity and a production can be to reduce costs.

(13) in form of ferroelectric capacitor manufacturing method according to the present embodiment, said 2005, oxidation in an atmosphere in is ([...]) is embodiment where the thermal treatment is performed, said PZTN composite oxide condition in a process of thermal treatment is performed at amorphous until may be proposed.

According to this aspect, until be crystallized 2005 and which is amorphous state. To this end, in ferroelectric-like low is, capable of forming a protection film until stable amorphous state by crystalline quality by the diffusion can be is prevented from deterioration of the light. And, -crystalline state, which state is 2005, is where the thermal treatment is performed in an atmosphere in oxide device is embodiment, oxygen in film constitution: have been introduced. To this end, to a heat treatment for crystallization state at the time of, contained in the atmosphere gas without dependence on the type PZTN composite oxide crystallization can be performed.

(14) in manufacturing method of ferroelectric capacitor according to the present embodiment form, as slicon oxide film contains a fluorescent substance capable of said, tree can be formed using methyl thread column.

According to this aspect, oxide for forming silicon film generally used compared to agent composed of [...] (TEOS), methyl thread column tree with little hydrogen generated during process (TMS) using slicon oxide film into the bottom structure in a control gate is formed on the, discharge by reduction using to ferroelectric can.

(15) in manufacturing method of ferroelectric capacitor according to the present embodiment form, of crystallizing the composite oxide said PZTN the heat treatment for non-oxidizing atmosphere is used..

According to this aspect, a heat treatment for crystallization to be in non-oxidizing atmosphere, for example in-process device surround member other than capacitor (for example, metal wiring) even when including, such peripheral members, to retain a 1 frame Image from 1 high temperature heat treatment constitution: a can be.

(16) the present embodiment in the form of a ferroelectric capacitor, said is of the ferroelectric capacitor is formed by using a manufacturing method.

(17) in addition, the present embodiment a ferroelectric capacitor a ferroelectric layer, and an in the form of, a ferroelectric memory using same, piezoelectric element, and semiconductor that it can be applied to an..

Hereinafter, suitable embodiment for the type the present invention, a reference to the drawing described more specifically.

1. Ferroelectric, ferroelectric capacitor, and their manufacturing method

Figure 1 shows a form of the present invention embodiment also ferroelectric according to (101) using a ferroelectric capacitor (100) is a cross section shown mimetic a.

As shown in the 1 also, ferroelectric capacitor (100) the ferroelectric (101), number 1 electrode (102), and number 2 electrode (103) consists of in.

Number 1 electrode (102) and number 2 electrode (103) the, Pt, Ir, said or a simple substance of a noble metal such as Ru mainly consists of noble metal. of a composite material based on a. Number 1 electrode (102) and number 2 electrode (103) to ferroelectric element and electrode is diffused (101) interfacing portion of the composition a plurality pixels has since deterioration of square hysteresis, number 1 electrode (102) and number 2 electrode (103) the ferroelectric elements-not-spread in fineness is is required. Number 1 electrode (102) and number 2 electrode (103) in order to have in fineness of a, for example a rare gas sputter depositing a heavy mass method, Y, La distributed to one of the electrodes and a noble metal oxide such as a record head capable of going method is to be taken..

Ferroelectric (101) the, Pb, Zr, Ti as constituent elements PZT-based high frequency induction heater and apparatus including oxides is formed. In particular, in the present embodiment, is ferroelectric (101) of Nb doped with Ti site Pb (Zr, Ti, Nb) O₃ (PZTN) characterized in that employing.

The Nb Ti and a size (ionic radius is nearly the same as the size of, an identification the atomic radius) which as a kind of electric charge like, weight are often crucial 2 times the cross-, grating due to vibration atoms frame through hooks it is difficult to are disengaged to atoms from the grate even. The valency of in addition Nb, stable transverse +5, e.g. Pb even is desorbed, Nb⁵⁺ by Singer of Pb. can replace. In addition to amorphous, even if the issuer generating the hinge pole Pb, and large-sized than are disengaged to O, small Nb:1. the side is put.

Furthermore, the valency of Nb since are present in the substrate alloy is + 4, Ti⁴⁺. capable of performing sufficiently instead. Furthermore, Nb actually covalent bonding property are very strong against, and is less susceptible to Pb also leaving the is think (H. Miyazawa, E. Natori, S. Miyashita; Jpn. J. Appl. Phys.39 (2000) 5679).

Still isn, Nb doping PZT to, the scan electrode driver applies a Zr mainly if the royal tomb the body really region but way, thereby, the quantity of 0.2 ∼ 0.025mol % (J. Am. Ceram. Soc, 84 (2001) 902 ; Phys. Rev. Let, 83 (1999) 1347) to, is very low quantities. Nb and the factor of enterpriser can doped high levels of the, addition of, for example, in an Nb 10mol %, has a crystallization temperature during cooling of 800 °C rises above an upper is think it is caused by the to.

Therefore, ferroelectric (101) for when forming, in addition PbSiO₃ silicate, for example is added to ratio of 1 ∼ 5mol % it is preferable that the. Energy for crystallizing the PZTN. it possible to reduce the number. I.e., ferroelectric (101) when using a PZTN as the material of, agents with addition Nb, PbSiO₃ crystallization temperature of PZTN by adding silicate wound around the first column-type.

Next, the present embodiment in the form of ferroelectric capacitor (100) PZTN ferroelectric applied to (101) a film-forming one example of the described method.

PZTN ferroelectric (101) the, Pb, Zr, Ti, Nb and raw material liquid including number 1 ∼ number 3 at least one of a step of preparing a solution by the catalyst comprises a mixed in, these mixture included in an oxide heat treatment is operated formed. can be obtained by.

Number 1 as raw material liquid, ([...]) PZTN ferroelectrics as a matter of at are made of silver, by Zr and Pb PbZrO₃ perovskite for forming the crystal, such as-butanol n condensation polymerization body the dissolving the at state in solvent solution can be exemplified.

Number 2 as raw material liquid, at-constituting metals ferroelectrics coat PZTN, by Ti and Pb PbTiO₃ perovskite for forming the crystal, such as-butanol n condensation polymerization body the dissolving the at state in solvent solution can be exemplified.

Number 3 as raw material liquid, at-constituting metals ferroelectrics coat PZTN, by Nb and Pb PbNbO₃ perovskite for forming the crystal, such as-butanol D condensation polymerization body the dissolving the at state in solvent solution can be exemplified.

Said number 1, number 2 and number 3 using raw material liquid, for example PbZr_0.2 Ti_0.6 Nb_0.2 O₃ (PZTN) ferroelectric consisting of (101) are formed on a, (raw material liquid number 1) : (number 2 raw material liquid): =2 (raw material liquid number 3): .and may be incorporated into a, at a ratio of 6:2. However, a speed of n times mixed solution is crystallized even attempts, PZTN ferroelectric (101) for the production of said, time as large as that of high crystallization temperatures necessary. I.e., solvent and mixed, Nb, is has a crystallization temperature during cooling of sharply increases and, of 700 °C hereinafter either a circular or rectangular cross-crystallization performed to store temperature, the Nb or more 5mol % the element substituted they are not being used as a Ti, didn't the current source from deviating steps of additive until now. Addition, Ti is a seed containing large than Zr in tetragonal PZT cannot e.g. no. This, J reference literature. Am. Ceram. Soc, Phys or 84 (2001) 902. Rev. Let, 83 (1999) 1347 clear by carried out, the amount of shift.

Therefore, in the present embodiment, it achieves the object of designing said, number 4 as raw material liquid, PbSiO₃condensation polymerization body the for forming the crystal, such as n-butanol solution dissolving the at state in solvent, for example less than 5mol % 1mol % or more further be effective for whitening, for treating said can be overcome by adding a.

I.e., said number 1, number 2, number 3 and number 4 by using a mixed solution of solution, a crystallization temperature of 700 °C hereinafter PZTN capable of being of crystallizing a temperature range, starting rotation is carried out, the amount is.

Specifically, also ferroelectric the flexible bumper structure for flow shown in the 2 (101) there can be reduced. Mixed solution coating process (step ST11), alcohol removal process heat treatment process drying ∼ ∼ degreasing heat treatment process (step ST12, ST13 step) a second series of steps of a desired number of times is performed, then by crystallisation annealing (step ST14) is obtained by multiplying a ferroelectric (101) is formed on.

An example of conditions in a each process shown in a..

First, on a substrate for electrode of Si Pt such as noble metal coated on a lower electrode (step ST10) there can be reduced. Next, space for recalling the mixture produced through coating-fluid application such as spin coating application, the portable telephone sends (step ST11). Specifically, mixing solution is dripped Pt on a substrate covered with an. Loaded solution to a substrate front the purpose to spread out the liquid by winding the spin can 500rpm to, reduces the rpm to 50rpm hereinafter to rotated by 10 seconds. Drying thermal process carried out in 150 °C ∼ 180° C (step ST13). Atmospheric heat treatment is drying, for example by hot plate under, the portable telephone sends. Similarly degreasing heat treatment step on hot plate that is kept 300 °C ∼ 350° C, atmospheric carried out under (step ST13). The baking crystallization, oxygen atmosphere, for example by rapid thermal annealing (RTA), the portable telephone sends (step ST14).

Film thickness of sintered in addition can be is adjusted to about 100 ∼ 200 nanometer. Next, by sputtering, the upper electrode after formation of the form, so (step ST15), interface forming with ferroelectric thin film electrode and number 2, and a ferroelectric film by using a for enhancing crystallinity of post annealing or the like different from one another, as well as upon firing, oxygen atmosphere of utilizing the novel peptide or the RTA is performed (step ST16), ferroelectric capacitor (100) to obtain.

In hereinafter, PZTN ferroelectric (101) to a ferroelectric capacitor using (100) with the influence on the gain varied amount of an amplifier to. reviews.

Also Figure 3 shows a ferroelectric capacitor (100) of P (polarization)-V (voltage) hysteresis curve. the shown mimetic. First, voltage + Vs application polarization amount P (+Vs) and, then, voltage is 0 as the polarization amount Pr. Furthermore, when to -1/3 Vs voltage, polarization P is the amount (-1/3Vs). And, when Vs-voltage the amount the polarization P (-Vs) and, when O voltage again the electrode is Pr-amount. Furthermore, the when + 1/3 Vs voltage, polarization the amount P (+1/3Vs) and, when again to + Vs voltage, polarization amount is again. returning P (+Vs).

Furthermore, ferroelectric capacitor (100) the, hysteresis characteristics has enhanced skin such as hereinafter. First, once voltage Vs by applying a polarization amount after a P (+Vs), -1/3 Vs voltage is applied, when in that 0 applying voltage in addition, hysteresis loop trajectories represented by Figure 3 during arrow A referred, polarization the amount PO (0) has a stable value has. Furthermore, amount of polarization by applying a Vs voltage-once (-Vs) after a P, +1/3Vs voltage is applied, when in that 0 applying voltage in addition, hysteresis loop trajectories represented by Figure 3 during arrow B referred, polarization the amount has a stable value PO (1) has. The polarizing amount PO (0) and polarization amount PO (1) if word of high frequency sufficiently of the support, with the difference, said disclosure Official Gazette call 9-116107 [...] a driving method or the like simple matrix type ferroelectric memory device by activating an..

And, the present embodiment in the form of ferroelectric capacitor (100) according to, low-temperature crystallization temperature, having improved of square hysteresis, can attain improvement to Pr. Furthermore, ferroelectric capacitor (100) by an improvement in-of square hysteresis, simple matrix ferroelectric memory device for driving the capacitors are shared important for stability of interference to the body. is eminently. In simple matrix type ferroelectric memory device, write, read-out not even the cells since the diabetes-voltage of ± 1/3 Vs, this voltage-polarizable not from the resistance calculated from the resistance, called interference characteristic, it is necessary that stable. Actually, in the invention herein in general PZT polarization is in a stable state, in the direction in which the shift polarization from 1/3 Vs pulse 10⁸ times the amount polarization kinds are fed through but appears lowering degree of 80%, the present embodiment in the form of ferroelectric capacitor (100) according to the amount of degradation of a 10% hereinafter it has been confirmed. Therefore, the present embodiment in the form of ferroelectric capacitor (100) a ferroelectric memory device that needs to be applied to the, simple matrix type memory practical. of the.

To hereinafter, the present embodiment of the physical shape therefore, the embodiment described the thereby, the cold air flows.

(In the embodiment 1)

The present in the embodiment in, compares a a of the existing method PZT and invention according to PZTN herein. Film forming flow in aforementioned all by using 2.

Pb:Zr:Ti:Nb=1:0 . 2:0 . 6:0 . 2, 1:0.3:0 . 65 1:0.2:0 . 7:0 . 1 and: light with the 0 . 05. I.e. light with the entire 5 ∼ 20mol %, by weight, of Nb. Herein PbSiO₃ 0 ∼ 1% of added.

The surface of the film morphology of Figure 4 A ∼of Figure 4 C. shown in. Furthermore, crystallinity of the film by measuring the X ray in the diffraction law , shown in the of Figure 5 A ∼of Figure 5 C and equal. 0% (no) which are drawn on the of Figure 5 A when, even when a plate until 800 °C, paraelectric pyrochlore fine only is composed of. Furthermore, when 0.5% which are drawn on the of Figure 5 B, with claw word meaning fine and a PZT was mixed. Furthermore, when 1% which are drawn on the of Figure 5 C, PZT (111) oriented single been second layer. Also crystalline in addition is not obtained until now resulted in smaller dimensions was preferred.

Next PbSiO₃ PZTN thin film to 1% of added, result on 120 ∼ 200 nanometer film thickness, as shown in the of Figure 7 A ∼of Figure 7 C and of Figure 6 A ∼of Figure 6 C, proportional film thickness each showed than conventional, the crystallinity. Also, the of Figure 6 A ∼of Figure 6 C, surface 120 nanometer ∼ 200 nanometer film thickness and electron micrographs shown in the morphology, in membrane thickness has of Figure 7 A ∼of Figure 7 C 120 nanometer ∼ 200 nanometer PZTN thin film crystalline indicating a X ray in the diffraction law is, the measured results by. Furthermore, as shown in the of Figure 9 A ∼of Figure 9 C and of Figure 8 A ∼of Figure 8 C, film thickness is 120 nanometer ∼ 200 nanometer range of the door of a square in both this method enables an accurate the gain varied amount of an amplifier. Also, the of Figure 9 A ∼of Figure 9 C, features enlarged of a curve of Figure 8 A ∼of Figure 8 C hysteresis. In particular, as shown in the of Figure 9 A ∼of Figure 9 C, present in thin film PZTN example, esters of phenylenedialkanoates as inhibitors by 2/2-way valves, which low voltage 2V an improper opening and, in addition and saturated, is showed.

Furthermore, even for leak characteristics, as shown in the of Figure 10 B and of Figure 10 A, improved regardless of the thickness of the film composition or film thickness, (in saturation) to 2V upon application 5×10^-8 ∼ 7×10^-9 A/cm2 was very good.

Next, PbZr_0.2 Ti_0.6 Nb_0.2 fatigue property of thin film, and static imprint, determined, as shown in the of Figure 11 B and of Figure 11 A, was very good. In particular, the fatigue property, as shown in of Figure 11 A, upper/lower electrode using although Pt to, .very good.

Furthermore, also as shown in the 12, substrate (601) on, lower electrode (602), the present embodiment the first deoxygenator PZTN ferroelectric (603), upper electrode (604) is formed a ferroelectric capacitor (600) by ozone TEOS on SiO₂ film (605) for forming made an attempt to. From conventional PZT by the ozone TEOS SiO₂ when anti-, the upper hydrogen generated from TEOS Pt through the PZT to, completely exhibiting hysteresis have, PZT is set determined constitution: it is known to.

Outputted PZTN ferroelectric: an embodiment (603) the, also as shown in the 13, and does not deteriorate with substantially, with hysteresis, which has the good. I.e., the present embodiment: an PZTN ferroelectric (603) the non-reducing even a strong could see he. Furthermore, invention according to tetragonal PZTN ferroelectric herein (603) is Nb in 40mol % when does not exceed, addition amount of Nb according to hysteresis were achieved for good.

Next, for comparison of the existing method PZT was unit photographs a ferroelectric. Conventional as PZT, each Pb:Zr:Ti=1:0 . 2:0 . 8, 1:0.3:0 . 7, and light with the 1:0.6:0 . 4. Property leak of the same, also as shown in the 14, the leak characteristics of a V content Ti is simply, Ti: when 80%, a width of the 2V, 10^-5 A/cm2 and, being not adapted to applications memory could see he. Fatigue as well as also characteristic of a transfer system 15 as shown in the, Ti he, the degraded characteristics fatigue of a V content. Also after the imprint in addition as shown in the 16, does not substantially data is read out can be viewed.

Or more in the embodiment understructure is found in, the present embodiment: an PZTN 2005, conventional, are considered caused essentially PZT leakage current increase and imprint characteristic deterioration as as well as to used to solve the problem, until now, are not used in the reason, tetragonal PZT type of a memory, by structure to its use in use memory without rotation is carried out, the amount is. Addition, same reasons PZT tetragonal from the use in communication with a piezoelectric element electrodes are implemented separately from one another applicable material comprising a host material and a..

(In the embodiment 2)

The present in the embodiment in, PZTN formed on the substrate, is changed to 0, 5, 10, 20, 30, 40mol %, by weight, of Nb bsto and compared. All in a sample PbSiO₃ added 5mol % silicate. Furthermore, anti-of raw materials, for the is compared with the for forming ferroelectric film of the sol-gel solution for the formation, by the addition of methyl succinic is a pH 6. Film forming flow using 2 in aforementioned all of wet liquid to flow down.

19 to also 17 ∼ also, the present embodiment the first deoxygenator PZTN ferroelectric. shown provided to amplify the measuring.

As shown in the of Figure 17 A, when Nb addition ratio of 0, but obtained esters of phenylenedialkanoates as inhibitors leakage, as shown in the of Figure 17 B, when 5mol % addition ratio of Nb, having a high insulation property good much as the gain varied amount of this method enables an accurate.

Furthermore, as shown in the of Figure 18 A, ferroelectric properties, until 10mol % addition ratio of Nb, scarcely changed with no visible was. Nb addition ratio of 0 in even in the case, but leakage of, didn't is seen in the ferro electric propertiescopyright 2000. Furthermore, as shown in the of Figure 18 B, the when 20mol % addition ratio of Nb, very square having a good shape as the gain varied amount of an this method enables an accurate.

However, as shown in the of Figure 19 B and of Figure 19 A, 20mol % addition ratio of Nb exceeds a, much as the gain varied amount of the largely varying in the, it was found from being degraded.

Therefore, X ray diffraction pattern also bar comparing the signal-to-as 20. 5mol % addition ratio of Nb (75/5/Nb=20/Zr/Ti) when, (111) a peak location, with additive Nb from conventional PZT but does not change sometimes not reflective, 20mol % addition ratio of Nb (60/20/Nb=20/Zr/Ti), 40mol % (40/40/Nb=20/Zr/Ti) according to by of increasing to, (111) he of not only shifting of the base angle side the picks. I.e., Ti composition of PZT tetragonal many is in spite of the region, the decision of actual if the royal tomb the body really crystal plates are formed by supporting can be viewed. According to mirror is constructed crystalline in addition, the capacitor is varies in a can be viewed.

Addition, Nb for 45mol % added bar, without an open hysteresis, ferroelectric identifies characteristics could not be applied to (not shown).

Furthermore, invention according to PZTN film herein, very having a high insulation property if the regular time but already described, is the insulation PZTN wherein conditions determined the present bar, also as 21.

I.e., invention according to PZTN film herein, very having a high insulation property a, the convexity on the Pb this significant defect in amount of a composition ratio 2, Nb added to Ti site is enabled. Furthermore, 22 which are drawn on the perovskite determination is also WO₃ can see changes in the crystal structure of collected and even, may and defect 100% ion site A and established, in addition WO₃ crystalline the easily changes. is known.

Therefore, PZTN respectively, by adding a Nb, Pb defect packaging cans and controlling the amount, controls to distribute and supply the main crystalline in addition is enabled.

This, the present embodiment in the form of PZTN film, piezoelectric element which can very effectively ameliorate even application in indicating of wet liquid to flow down. Generally, the piezoelectric element PZT when refresh of frame, the scan electrode driver applies a Zr use of region if the royal tomb the body really composition. At this time, the scan electrode driver applies a Zr based PZT. called soft PZT. This character directly, means a soft determination is. For example even discharge nozzle of ink-jet printer using ultrasonic, but using the PZT-based soft, since the soft so , too high viscosity in ink, in pushed by of can't passing out.

While, the scan electrode driver applies a Ti the hard-type PZT tetragonal PZT the called, the rigid frangible means. However, films and hard-type circuit turns on/of the invention PZTN herein, is changed in a crystalline artificial tan to if the royal tomb the body really it is possible to. Furthermore, crystalline a addition amount of Nb by randomly with respect and capable of changing, in addition Ti the scan electrode driver applies a of the sintered compact dielectric constants 2005 based PZT, board to drive by on a low-voltage device can be..

The, now of enterpriser is used up to the end, a PZT hard-type, for example of ink-jet printer using ultrasonic discharge nozzle is to its use in rotation is carried out, the amount. Addition, the Nb not flowed in by sealing softness to PZT, conveniently the hard, frangible PZT not capable of providing is carried out, the amount of.

Finally, until now invention as described above wherein, in the present in the embodiment as well as the addition of Nb, Nb is added simultaneously, by adding a silicate, .can be reduced but the temperature crystallization.

(In the embodiment 3)

The present in the embodiment in, for example memory cell power consumption of the ferroelectric memory or ferroelectric capacitor between the, for example between the discharge nozzle of ink-jet printer using ultrasonic electrode material of the piezoelectric actuator or Ir Pt in which these compounds are used as a metallic platinum group metal such as on PZTN integrity grating when the film is formed in effectiveness to that using membranes PZTN examined. The platinum group metal, when PZT-based ferroelectric application device, for determining the crystal orientation of a ferroelectric with base film in, material having useful as electrode material. However, of both induced by the insufficient in compatibility grating, with regard to application device, ferroelectric been partially sealed by the fatigue property.

Therefore, the inventor herein, elements constituting Nb during PZT-based ferroelectric by to include, between thin film platinum group metal cleaning solution based PZT lattice mismatches has been developed a technique for is improved. In this case of Figure 23 A ∼of Figure 23 C film-forming step wherein a ferroelectric-based PZT. shown in.

First, as shown in the of Figure 23 A, substrate exposed to the outside (11) for preparing a. Substrate (11) as, SOI TiOx layer is formed on a substrate the ground terminal of a. Also, substrate (11) as, publicly known a material arranged to at least suitable for a select to ID.

Next, as shown in the of Figure 23 B, substrate (11) on, for example by sputtering a metallic film (number 1 electrode) Pt (102) is formed, as shown in the of Figure 23 C then, metal film (102) on extended into a predetermined (101) as PZTN connection hole through a filling. PZTN for forming a film material is, for example can be using sol-gel solution for the formation. More specifically, PbZrO₃ for sol-gel solution for the formation, PbTiO₃ for sol-gel solution for the formation, and PbNbO₃ for to mixing a sol-gel solution for the formation, in addition PbNbO₃ by adding sol-gel solution for the formation for use. Yet, PZTN film, , because it includes the elements constituting Nb to, has a crystallization temperature during cooling of high.. To this end, for to reduce crystallization temperature, PbSiO₃ further sol-gel solution for the formation for using the added it is preferable that the. The present in the embodiment in, said Pt metal film of a sol-gel mix solution which is then (102) and method and spin coating on, a predetermined heat treatment performed determined the. The flow of process of film-forming and thus, also is similar to the shown in the 2.

The present in the embodiment in, , the amount of the Nb 0mol % ∼ 30mol % a been obtained on the range of PZTN film, X ray diffraction method of determined using the lattice constant, determined, of Figure 24 A and of Figure 24 B and a equal. According to of Figure 24 B and of Figure 24 A, middle of addition ratio of of Nb, a axis (or b axis) in axis c lattice constant in lattice constant is accessed it is found that the can. Furthermore, in the V (abc) of Figure 24 A, a lattice constant (a, b, c) is indifferent indexes level. Furthermore, during of Figure 24 A V/V₀ the, not with additive Nb PZT crystal lattice constant indifferent indexes level V₀ upon determination PZTN for a. bead with V (abc). As such, V (abc) or V/V₀ even email widow, a web page or, PZTN determination is, Nb of addition ratio of by lowering a clear level Image in accordance with the signal to pass through the crystal lattice capable of confirming the..

And, and Nb for formed by the addition of PZTN from lattice constant of the film, Pt metal layer with lattice constant (a, b, c=3.96) lattice mismatch between a calculated the total ratio addition amount of Nb (mol %) for transversely to the plot is shown in 25 also is formed. Also according to 25, the fram based PZT includes the effect of the Nb, examples of the such as the above-mentioned each embodiment as well as the capacitor is formed on the protection layer and the, Pt lattice constant thereof such as platinum group metal crystal lattice constant close to showed 50. In particular, Nb 5mol % addition ratio of of in or more regions, and its effect is significantly it was observed that shown.

Therefore, the surface of the substrate of the present invention method, electrode re lattice mismatch between a between ferroelectric metal film is exposed to the outside are alleviated ROM for storing programs, for example in 30mol % addition ratio of of Nb, the total ratio lattice mismatch between a 2% it was observed that improved extent. This, PZTN of crystal structure, Nb Ti atoms B site-up Image and an ionic bonding property between atoms O atoms covalent bonding property and a strong bond therebetween which is generated, having, the same direction for compressing a crystal lattice to improve purity and acts, to pass through the lattice constant is changed in a direction of which are considered to be..

Furthermore, chemically platinum group metal such as Pt stable as a material, ferroelectric memory or a piezoelectric actuator suitable material of electrodes, the present embodiment the first deoxygenator according to method, is PZTN Pt metal film directly on the magnetic film, and relax the lattice mismatch greater than in the prior art for tire formation that realizes not only, the objective compound. a barrier layer. Therefore, the present embodiment the method the first deoxygenator, PZT-based ferroelectric fatigue deterioration the reducing, ferroelectric memory or a piezoelectric actuator is also suitable for application of a printed layer can be wall of the rectangular.

(Reference example)

The present in PbZr_0.4 Ti_0.6 O₃ ferroelectric film.

In of the existing method method, including degree 20% excessive titanium in which using a solution of Pb, Pb volatile this number the temperature reduction and crystallization inhibitors of. However, a thin film formed in excess Pb is, what the ambiguous whether a, inhibits the excess amount of at least original Pb. must.

Therefore, excess Pb is 0, 5, 10, 15, 20% in 10% weight concentration of PbZr_0.4 Ti_0.6 O₃ for forming sol-gel solution for the formation (solvent: n-butanol) using, in addition 10% weight concentration of PbSiO₃ for forming sol-gel solution for the formation of (solvent: n-butanol), by adding 1mol % each, shown in steps ST20 ∼ step ST25 26 also each by a screw thread, of 200 nanometer PbZr_0.4 Ti_0.6 O₃ the front/rear sides of the ferroelectric. The surface wool Polo of Figure 27 A ∼of Figure 27 C shown in the same as the, XRD pattern of Figure 28 A ∼of Figure 28 C shown in equal.

The resonator receives a 20% a, particularly excess degree necessary for Pb, a Pb, particularly excess 5% is sufficiently crystallization progress can be are shown. This, slightly 1mol % of PbSiO₃ catalyst is, because lowering of the crystallization temperature of PZT, the Pb and requires little whether or not the excess of wet liquid to flow down. After this, PZT, PbTiO₃, and PbZrTiO₃ as solution for forming, using a solution of 5% Pb both excess of wet liquid to flow down.

Next, 10% weight concentration of PbZrO₃ for forming sol-gel solution for the formation (solvent: n-butanol) and 10% weight concentration of PbTiO₃ for forming sol-gel solution for the formation of (solvent: n-butanol) in a weight ratio of 4:6 to a solution concentration of 10 weight % PbSiO₃ for forming sol-gel solution for the formation of (solvent: n-butanol), using the supplying 1mol % of Figure 2 respectively, 200 nanometer-PbZr_0.4 Ti_0.6 O₃ ferroelectric film. The, hysteresis characteristics, as shown in the of Figure 29 B and of Figure 29 A, to open the door of a square. However, it has also been found a leakage simultaneously.

Furthermore, for comparison, of the existing method method in, the aforementioned of Figure 26 for use with a flow the, 10% weight concentration of PbZr_0.4 Ti_0.6 O₃ for forming sol-gel solution for the formation (solvent: n-butanol) to 10 weight % concentration of PbSiO₃ for forming sol-gel solution for the formation of (solvent: n-butanol), using the supplying 1mol %, 200 nanometer-PbZr_0.4 Ti_0.6 O₃ ferroelectric thin film was produced. At this time, hysteresis characteristics, as shown in the 30 also, hysteresis good much did not obtained.

Therefore, the removable memory using ferroelectric film and each a gas analysis, of Figure 31 A and of Figure 31 B and a equal.

As shown in the of Figure 31 A, PZT sol-gel solution for the formation of the existing method 2005 the memory, the for temperatures of up to about 1000 °C from room, always attached to the degassing C or H were identified.

While, as shown in the of Figure 31 B, 10% weight concentration of PbZrO₃ for forming sol-gel solution for the formation (solvent: n-butanol) and 10% weight concentration of PbTiO₃ for forming sol-gel solution for the formation of a 4:6 (solvent: n-butanol) using a solution of light from the LED and radiating the ferroelectrics just is when the invention according to herein, substantially until break down the degassing is not visible can be viewed.

This, concentration of 10 weight % PbZrO₃ for forming sol-gel solution for the formation (solvent: n-butanol) and 10% weight concentration of PbTiO₃ for forming sol-gel solution for the formation of 4:6 (solvent: n-butanol) of waves of water vein by using a, initially be effective for whitening, for treating weight 10% concentration of PbTiO₃ for forming sol-gel solution for the formation (solvent: n-butanol) by on Pt PbTiO₃ is crystallized is, this is into the nucleus initial is determined, in addition Pt PZT and transfers the selected lattice mismatch, PZT easily been considered to be crystallized. Furthermore, by using a mixed solution, PbTiO₃ and a PZT is a good interface is continuously formed at the, good-of square hysteresis is considered to be connected.

2. Manufacturing method of ferroelectric capacitor

The of Figure 32 A ∼of Figure 32 C, according to one example of process for manufacturing ferroelectric capacitor of the present invention embodiment form shown mimetic a is a cross-sectional drawing.

(1) first, as shown in the of Figure 32 A, exposed to the outside (110) thereupon a lower electrode (102), ferroelectric (101), upper electrode (103) form are sequentially formed.

Gas (110) as, for example semiconductor substrate, resin according to use ferroelectric capacitor such as a substrate suitable for the may employ optionally, has is not particularly limited in.

Lower electrode (102) and an upper electrode (103) as, for example Pt, Ir, said or group a noble metal such as Ru of a composite material based on a mainly consists of noble metal for practicing the method comprising a can be. Also, lower electrode (102) and an upper electrode (103) the, for example film-forming method such as deposition or sputtering, the publicly known can be is formed by an. Furthermore, lower electrode (102) and an upper electrode (103) to elements constituting ferroelectric and electrode is diffused (101) at an interface part facing composition is of square hysteresis when a mode is cause shift reaction gas is lowered and the water, lower electrode (102) and an upper electrode (103) the water flowing into the water tank and is diffused elements constituting ferroelectric cell is reduced even if the in fineness is request. Therefore, lower electrode (102) and an upper electrode (103) to increase in fineness of, a rare gas sputter depositing a heavy mass or method, Y, La dispersed in noble metal electrode oxide such as a record head capable of going which may employ method.

Ferroelectric (101) the, Pb, Zr, Ti, Nb and including as constituent elements, called PZTN is composite oxide. Furthermore, ferroelectric (101) the, Pb, Zr, Ti, Nb for including sol-gel solution for the formation of, for example spin-coating, for example by lower electrode (102) on can be formed by applying a. Such as sol-gel solution for the formation, by Zr and Pb PbZrO₃condensation polymerization body the for forming the crystal, perovskite n-butanol a dissolving the at state in solvent such as number 1 sol-gel solution for the formation, at-constituting metals PZTN ferroelectric on, by Ti and Pb PbTiO₃condensation polymerization body the for forming the crystal, perovskite n-butanol a dissolving the at state in solvent such as number 2 sol-gel solution for the formation, and at-constituting metals PZTN ferroelectric on, by Nb and Pb PbNbO₃ perovskite condensation polymerization body the for forming the crystal, such as n-butanol number 3 a dissolving the at state in solvent mixing a sol-gel solution for the formation can be using. Furthermore, ferroelectric (101) for when forming, a low crystallization temperature of composite oxide PZTN in order to allow a, silica (germanate) for including audio/video RF transmitter germanium kate or may addition of sol-gel solution for the formation. Specifically, for example PbSiO₃condensation polymerization body the for forming the crystal, n-butanol a dissolving the at state in solvent such as number 4 sol-gel solution for the formation of, for example less than 5mol % 1mol % or more said mixed sol-gel solution for the formation is more can add. Such number 4 sol-gel solution for the formation by mixing, crystallization by Nb is included in elements constituting tubes is 700 °C hereinafter PZTN composite oxide a plate capable of being of crystallizing a temperature range, starting rotation is carried out, the amount is.

Furthermore, ferroelectric (101) the, applied such PZTN atmosphere oxide film would prevent a crystallized or more complex oxide (for example, 400 °C hereinafter) to the heat treatment in a heat-treating, by identifying the state of a PZTN composite oxide a crystallization accelerating material. it is preferable that. The, ferroelectric (101) prepared while reducing manufacturing cost is amorphized free of state the fitting projection, while prevents diffusion of elements constituting refers to can be coating a photosensitive solution. Furthermore, a load is the it atmosphere oxide heat treatment, after capable of forming a protection film refers to in order to determine composite oxide PZTN supplies the oxygen required ferroelectric component (101), which also serves to in.

(2) next, as shown in the of Figure 32 B, lower electrode (102), ferroelectric (101), and an upper electrode (103) the desired shape machining on a substrate, by etching a, these so as to cover the, SiO₂ (silicon oxide) the protection layer (104) is formed on. At this time protective film (104) the, tree methyl thread column by CVD using (TMS) can be. Tree methyl thread column the (TMS), oxide for forming silicon film generally used compared to agent composed of [...] (TEOS), CVD is hydrogen amount generated during process, tree methyl thread column the surface of the substrate (TMS), ferroelectric (101) process by reduction using to identical, which in turn reduces the damage. Also, a protective film using (TMS) methyl thread column tree (104) a fabrication process of, using TEOS (forming temperature 400 °C or more) process for forming low temperature compared to (∼ 350 °C room temperature) since the enabling the sliding door to be opened, (1) in the processing of, ferroelectric (101) even when an amorphous state, such protective film (104) of a heat steps PZTN composite oxide is crystallized by in order to prevent the, . as it were and amorphous state.

(3) next, as shown in the of Figure 32 C, ferroelectric (101) constituting the PZTN of crystallizing the composite oxide performed the heat treatment for, PZTN ferroelectric crystalline films (101a) ferroelectric capacitor having may yield an. In is thermally treated, as well as oxygen atmosphere, for example Ar or N₂ non-oxidizing gas atmosphere such as due to an annealing in standby or determining composite oxide PZTN penetration hole while moving up and down.

Wherein, the present embodiment the manufacturing method in the form of lower electrode Pt, PZTN ferroelectric, Pt on a ferroelectric capacitor upper electrode using TMS SiO₂ respect to the semiconductor layer, such SiO₂ high PZTN capable of forming a protection film after heat treatment is performed in an oxygen atmosphere and stand-by mode into a crystallized of the capacitor and to the results measuring a characteristic hysteresis of Figure 33 B and of Figure 33 A. shown in. Oxygen has of Figure 33 A a moment when a heat treatment is performed in an atmosphere and shown, heating is performed in a standby of Figure 33 B found. it is shown a. According to of Figure 33 B and of Figure 33 A, oxygen atmosphere one of speed and stand-by mode even if heat-treatment in atmosphere, small resistance metal barrier layer even though the not formed is much as the gain varied amount of the door of a square this method enables an accurate. This, ferroelectric (101) is in an atmosphere in oxidation is formed where the thermal treatment is performed is crystallization embodiment pre-supplies the oxygen required since introduced into the film is. I.e., the present embodiment in the form of in manufacturing method, ferroelectric crystallization and does so without requiring the dependent to the atmosphere of the heat treatment can be. Furthermore, crystallization to a heat treatment for when the are performed in non-oxidizing gas atmosphere, power consumption of the ferroelectric memory refers to when the child is applied to the manufacturing method, other than capacitor surround member (for example, metal wiring) 1 frame Image from 1 high temperature heat treatment to constitution: a can be. Also, in this process a to a heat treatment for crystallization composite oxide PZTN, atmosphere is dependent of a gas species of, upper electrode (103) for connecting to a an external flat metal wire for forming protective film contact hole is (104) may formed on the carried out after the.

Furthermore, the present embodiment in the form of lower electrode Pt using manufacturing method, PZTN ferroelectric, Pt on a ferroelectric capacitor upper electrode using TMS SiO₂ the thickness of the, such SiO₂ capable of forming a protection film after crystallized to your high PZTN, SiO₂ for forming protective film temperature ambient temperature, 125 °C, as the gain varied amount of an even when an 200 °C, and comparison example SiO₂ without protective layer is formed on the crystallized PZTN ferroelectric hysteresis the sensing transistors placed and the second sheet is moved, the same of residual polarization amount 2Pr also result by measuring the shifted centering. shown in 34. According to also 34, SiO₂ passivation layer is room temperature, 125 °C, at least one out of one temperature either 200 °C residual polarization amount in a visible position without change in 2Pr, SiO₂ man5 glcnac2 stacked or combined with each other and is etched to form source and a sufficiently strong value is obtained a is produced it was observed that. I.e., the present embodiment in the form of in manufacturing method, temporary into (104) extended into a predetermined at the time of forming (101) generated during the process it also becomes possible to even when the with hydrogen, then for PZTN composite oxide crystallization by being thermal treatment is performed, this damage while regaining PZTN composite oxide is determined in this case, conventional ferroelectric the reset/sustain to (101) for reducing reaction for protecting against method of forming barrier film collector, a process, an improvement in productivity and a production can be to reduce costs.

3. Ferroelectric memory

The of Figure 35 B and of Figure 35 A, in only one of the present invention embodiment, the capacitors are shared simple matrix ferroelectric memory device (300) is shown in the configuration of drawing. The plane view of Figure 35 A, of the of Figure 35 B of Figure 35 A is taken along a A-A cross-sectional drawing. Ferroelectric memory device (300) the, as shown in the of Figure 35 B and of Figure 35 A, substrate (308) arranged predetermined number formed on word line (301 ∼ 303) and, predetermined number arranged bit line (304 ∼ 306) has. Word line (301 ∼ 303) and bit lines (304 ∼ 306) between the, said embodiment taught form consisting of PZTN ferroelectric (307) can be inserted and locked into the, word line (301 ∼ 303) and bit lines (304 ∼ 306) in the crossing region of the ferroelectric capacitor is formed.

Simple matrix is configured by the memory cells are arranged a ferroelectric memory device (300) in, word line (301 ∼ 303) and bit lines (304 ∼ 306) in the crossing region of the ferroelectric capacitor formed, write and read in and to the, the peripheral driving circuit not shown such as amplifier reading (them 'peripheral circuit' referred to as a), the portable telephone sends by. 'S a, on separate substrate memory cell array and MOS transistors to form a, word line (301 ∼ 303) and bit lines (304 ∼ 306) and may be connected to, or substrate (308) a monocrystalline silicon on both sides, peripheral circuit on the same substrate for array and a memory cell of a memory cell may also be integrated onto..

Figure 36 shows a embodiment in only one a are also peripheral circuit with a memory cell array on the same substrate for device (300) is integrated onto one example of a cross section is shown.

In Figure 36, single crystal silicon substrate (401) on MOS transistor (402) is formed, is is peripheral circuit part is transistor region. MOS transistor (402) the, single crystal silicon substrate (401), source, drain region (405), gate insulating layer (403), and a gate electrode (404) consists of by.

Furthermore, ferroelectric memory device (300) the, of device isolation oxide film (406), number 1 interlayer insulating film (407), number 1 wiring layer (408), and number 2 interlayer insulating film (409) has.

Furthermore, ferroelectric memory device (300) the, ferroelectric capacitor (420) has a storage cell array comprised of to, ferroelectric memory (420) the, a lower electrode is formed word line or a bit-by-bit lines (number 1 number 2 electrode or electrode) (410), including ferroelectric with ferroelectrics as a matter of on dielectric phase (411) ferroelectric (411) is formed on layer is covered with an upper electrode lines or word bit line (number 1 number 2 electrode or electrode) (412) consists of in.

Furthermore, ferroelectric memory device (300) the, ferroelectric capacitor (420) number 3 on interlayer insulating film (413) has, number 2 wiring layer (414) by, memory cell array and circumference circuit is section is connected to. Also, ferroelectric memory device (300) in, number 3 interlayer insulating film (413) and number 2 wiring layer (414) on are overlapped (415) is formed.

Around the rod by a Y-or more ferroelectric memory device (300) according to, memory cell array and circumference circuit by using the same substrate can be integrated on. Yet, also 36 device (300) nuclear fuel and composite burnable absorber shown in the, peripheral circuit part on memory cell array is formed is made but, well as peripheral circuit part on and is not disposed a memory cell array, memory cell array peripheral circuit part and a planar contacts may components, is.

The present embodiment used in ferroelectric capacitor (420) the, according to PZTN to form said embodiment, the circular flow channel property are very of square hysteresis, has coherent properties of stable. Furthermore, this ferroelectric capacitor (420) the, process temperature by peripheral circuit group or the like which is low in damages another element, damage process in addition (in particular the reduction of hydrogen) is, due to damage hysteresis which prevents the degradation of. Therefore, such ferroelectric capacitor (420) by using, simple matrix type ferroelectric memory device (300). of the practical.

In addition of Figure 37 A the, in an alternative form 1T1C-type ferroelectric memory device (500) of. it is shown a degree of structure. Of Figure 37 B has a ferroelectric memory device (500) is even with equivalent times.

Ferroelectric memory device (500) the, as shown in the of Figure 37 A, lower electrode (501), layer is covered with an upper electrode connected to plate (502), and using high PZTN ferroelectric embodiment in the form of (503) a capacitor (504) (1C) and a, source/drain electrodes one side of the data line (505) is connected to, to be connected to a word line gates that are connected electrode (506) for focus lens for transistor device (507) (1T) DRAM made of closely similar structure is of memory devices. 1T 1C 100ns hereinafter and reading write is used for high-speed there can be achieved, in addition since nonvolatile data written, SRAM substituted. for the evolution of or the like.

4. Power consumption of the ferroelectric memory manufacturing method

In hereinafter, " 2. Manufacturing method of ferroelectric capacitor " taught email widow, a web page or of power consumption of the ferroelectric memory manufacturing method for manufacturing method when it is applied to relates to.

The of Figure 38 A ∼of Figure 38 C, the process for manufacturing ferroelectric memory according to one example of the present invention embodiment form shown mimetic a is a cross-sectional drawing.

In the present embodiment, as shown in the of Figure 38 A first, gas (110) on ferroelectric capacitor (100) lower electrode of (102), PZTN ferroelectric (101), upper electrode (103) .are sequentially formed. The PZTN ferroelectric (101) the, oxide embodiment where the thermal treatment is performed is atmosphere and which is the amorphous state. Yet, gas (110) as, for example as shown in the of Figure 38 A, semiconductor substrate (111) on cell selection transistor (116) are corresponding to ID. The transistor (116) the, source/drain (113), gate oxide layer (114), gate electrode (115) can take the. Furthermore, transistor (116) on one side of the beer in source/drain (113) on the, for example tungsten a plug electrode (117) and thus forming the, ferroelectric capacitor (100) lower electrode of (102) a stack formed to be able to be connected function. Yet, gas (110) in, transistor (116) between the cell a device separation region (112) is separate hierarchies by, transistor (116) upper part of the, for example inter layer insulating film formed consisting of the oxide or similar films at (118) can take the.

Next, the present embodiment for production of step, as shown in the of Figure 38 B, ferroelectric capacitor (100) to a desired size and shape is patterned. Furthermore, ferroelectric capacitor (100) so as to cover the tree (TMS) using methyl thread column SiO₂ protective film (104) is formed, this contact hole for external connections on the (105) after formation of the form, so, the heat treatment in a heat-treating, high is crystallized PZTN, PZTN ferroelectric (101a) is formed on. In crystallization PZTN ferroelectric, the heat treatment for crystallized non-oxidizing atmosphere is used.. Image signal from outside, generates the, ferroelectric capacitor (100) surround member other than (for example, metal wiring) 1 frame Image from 1 high temperature heat treatment optical axis to form lights constitution: a can be.

And, the supply circuit switches sequentially the power, as shown in the of Figure 38 C, SiO₂ protective film (104) a transistor (116) contacts for connecting with the exterior and hole, metal line layer (191, 192) to obtain ferroelectric memory by forming a. According to process for production of the present embodiment, the films are only the reset/sustain ferroelectric (101) for reducing reaction for protecting against method of forming barrier film collector, a process, an improvement in productivity and a production can be to reduce costs. Furthermore, such method of forming barrier film having a good shape square of the monitored process having hysteresis characteristic ferroelectric capacitor (100), as it is hereby possible to form a, excellent characteristics of ferroelectric memory may yield an.

Yet, not to standardize the, called 1T1C type ferroelectric memory and manufacturing for the described but, the present embodiment in the form of the manufacturing method of ferroelectric capacitor, in addition, called 2T2C or simple matrix type (cross point-type) using various kinds of cell system a ferroelectric memory and manufacturing process can be applied.

5. Piezoelectric element and ink jet recording head

To hereinafter, in only one of the present invention embodiment, ink jet recording with respect to the head as further described..

Ink drops towards a discharge nozzles by opening portion of a pressure communication is composed of a diaphragm having a center bore, by piezoelectric elements of the diaphragm pressure generating but only deforms the nozzle opening by pressing the opening in the ink chamber from the outer chamber to the ink that droplets are discharged ink jet recording head has, extending in a direction axis of a piezoelectric element, to contraction of the member at the a longitudinal vibration mode piezo actuator and used in the range of, bending vibration mode piezo actuator 2 of used in the range of types of been employed in practice so of wet liquid to flow down.

And, bending vibration mode actuator as used in the range of, for example the entire surface of diaphragm by the techniques film forming over a piezoelectric is formed, processes for microlithography by the piezoelectric layer having a center bore pressure pattern that corresponds in shape to the to apply each having a center bore each pressure cutting the piezoelectric to it is known.

Also Figure 39 shows a ink jet recording head according to one embodiment of the present invention form multiplex and shows a decomposition perspective view, of Figure 40 A, the of Figure 39 plane view of Figure 40 B A-A and ' cross-sectional drawing and, Figure 41 piezoelectric element (700) is shown in the-layered structure including coarse. As shown in the, flow passage forming substrate (10) orientations in the present embodiment (110): a silicon single crystal, one side thereof is previously formed by thermal oxidation of silicon dioxide, micro 1 ∼ 2 thickness of elastic membrane m (50) is formed. Flow passage forming substrate (10) the, of a plurality of pressure having a center bore (12) is arranged in the width direction. Furthermore, flow passage forming substrate (10) having a center bore pressure (12) outside region longitudinal direction of connection pipe part (13) is formed, communication (13) and the pressure having a center bore (12) is, each pressure having a center bore (12) which is installed for ink supply passages (14) is cavities communicate through a. Also, communication (13) refers to the sealing board (30) driving a cart part (32) in communication with each pressure having a center bore (12) is of a common of ink chambers (800) composed of part of. Ink supply passages (14) the, pressure having a center bore (12) than formed in narrow width, communication (13) from having a center bore (12) flowing into the ink from a ink channel resistance of which realizes stabilizing of the.

Furthermore, flow passage forming substrate (10) of the if opening side , each pressure having a center bore (12) ink supply path of ink-(14) opposite side nozzle opening communicating the proximity of the end (21) is formed nozzle plate (20) through film or the like which for thermally or an antistatic as occasion demands is constitution: is secured.

While, such flow passage forming substrate (10) of opposite side of the living body when to trasmit asynchronous transfer mode, as described above, thickness, for example, about 1.0 micro m of elastic membrane (50) is formed, is elastic membrane (50) on the, thickness, like, for example, about 0.4 micro m of insulator film (55) is formed. Furthermore, is insulator film (55) on the, thickness, like, for example, about 0.2 micro m in lower electrode film (60) and, thickness, like, for example, about 1.0 micro m in piezoelectric layer (70) and, thickness, like, for example, about 0.05 micro m in upper electrode film (80) is, is laminate forming process refers to, piezoelectric element (700) .form a. Wherein, piezoelectric element (700) the, lower electrode film (60), piezoelectric layer (70) and upper electrode film (80) including a circulation promoted. portion. Generally, piezoelectric element (700) if one of the electrode as a common electrode and, as the other and piezoelectric layer (70) for each pressure having a center bore (12) each composed of by patterning. And, here patterned either electrode and piezoelectric layer (70) is composed, amount upon application of a voltage to electrodes is a new generation is distortion of the piezo active of the piezoelectric and the building. In the present embodiment, lower electrode film (60) in communication with a piezoelectric element (700) and common electrode of, upper electrode film (80) of an electrostrictive member device (700) but in that of individual electrodes, driving circuit or the wiring of same by pieces the't prevent troubles from occurring even when turned over. Even in the event of a one, each pressure active piezoelectric body each having a center bore is enabled unit is formed on a surface. Furthermore, here, piezoelectric element (700) and the associated piezoelectric element (700) for driving a diaphragm is generated displaced by combined ., called piezoelectric actuator. Also, piezoelectric layer (70) the, each pressure having a center bore (12) to apply each is made, as shown in the 40 also, ferroelectric multiple layers (71 (71a ∼ 71f)) are composed.

A ink jet recording head, ink cartridge and the like the ink channel communication recorder comprising the part of head unit, ink jet recording device is mounted on. Figure 42 shows a with their ink jet recording device is a coarse one example of it is shown a. Also 42 as shown in the, ink jet recording head a record head unit (1A, 1B) the, ink supply when the cartridge (2A, 2B) is detachably fitted to the pusher base and, head unit is recorded (1A, 1B) carriage equipped with the same, (3) the, device body (4) carry attached to pivot (5) the axial direction is mounted so as to be movable. Head unit is recorded (1A, 1B) the, for example each black ink composition and color ink composition disposed one upon the other and ejecting a. And, drive motor (6) the driving force of a not shown a plurality of gear and timing belt (7) through the carriage (3) transferring an to, recording head unit (1A, 1B) equipped with the same, computer carriage (3) has carry pivot (5) is move along. On the other hand, device body (4) carry the pivot (5) along the platen (8) is installed in the, not shown, such as by the supply roller the cleaning paper paper is a recording medium such as platen is S path of the recording sheet (8) is to be returned to on.

Yet, liquid injection head as ink discharge ink jet recording head as an example described but, the present invention refers to, piezoelectric element using liquid spraying head and liquid spraying device overall. communications intended for. As liquid injection head, for example ribbon cartridge writing the video of a recording head used in the device, liquid-crystal display or the like of color filter used in the production of colorant injection head, organic EL display, FED (surface-emission display) such as for forming electrode of an electrode used in the material injection head, used for manufacturing biochip a organic injection head or the like may, for example, in an.

The present embodiment in the form of piezoelectric element, suitable for a damascene piezoelectric film according to PZTN form said embodiment using the key, the free surfaces next effect can be achieved.

(1) piezoelectric ones covalent bonding property since the improved, the objective compound. a piezoelectric constant.

(2) defect in PbO piezoelectric ones since the can be suppressed, a piezoelectric layer is unlikely to separate at the interface between the electrode field is slid laterally so or more likely is an inverted can also form a multidimensional is, piezoelectric element as the objective compound. efficiency.

(3) since the are a piezoelectric layer is unlikely to separate, lno thin film penetration hole while moving up and down.

Furthermore, the present embodiment in the form of liquid spraying head and liquid spraying device a, said piezoelectric element including a piezoelectric layer by using a, in particular the free surfaces next effect can be achieved.

(4) a piezoelectric layer is unlikely to separate fatigue degradation since the can be reduced, a piezoelectric layer is unlikely to separate by suppressing the time-varying displacement amount, the objective compound. reliability.

At least, the present invention embodiment for the type described suitable but, the present invention refers to the semiconductor layer is without limit to an, various deformation embodiment can be in a range of from subject matter of invention embodiment can be by.

For example, ferroelectric (101) the, PZT to instead Nb Ta, W, V, even addition as adding Mo equal to or an organic solution and mixed with. Furthermore, Mn is added as can be employed in Nb as to simulate or an organic solution and mixed with. Furthermore, similar manner, order to prevent separation of connector roll Pb, Pb +3 or higher, has a for substituting the element of the is thought, their as candidate revisions, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, lanthanum such as Yb Lu and may to family orgin. Addition, an additive as crystallization, silicate (Si) germanium is not audio/video RF transmitter can be using (Ge). Of Figure 43 A to, Ta Nb to PZT 10mol % instead of adding the signal by in the use of heat shield as. shown. Furthermore, of Figure 43 B to, W Nb to PZT 10mol % instead of adding the signal by in the use of heat shield as. shown. Even when a Ta Nb is added equivalent effect can be achieved. it is found that the. Furthermore, both when using W hysteresis characteristics was achieved good in equivalent is added Nb using the interference pattern on the screen can be viewed.