THREE DIMENSIONAL NAND DEVICE CONTAINING FLUORINE DOPED LAYER AND METHOD OF MAKING THEREOF
The present disclosure relates generally to the field of semiconductor devices and specifically to three dimensional vertical NAND strings and other three dimensional devices and methods of making thereof. Three dimensional vertical NAND strings are disclosed in an article by T. Endoh, et. al., titled “Novel Ultra High Density Memory With A Stacked-Surrounding Gate Transistor (S-SGT) Structured Cell”, IEDM Proc. (2001) 33-36. An embodiment relates to a monolithic three dimensional NAND string including a semiconductor channel, at least one end part of the semiconductor channel extending substantially perpendicular to a major surface of a substrate and a plurality of control gate electrodes extending substantially parallel to the major surface of the substrate. The plurality of control gate electrodes include at least a first control gate electrode located in a first device level and a second control gate electrode located in a second device level located over the major surface of the substrate and below the first device level. The first control gate electrode is separated from the second control gate electrode by an insulating layer located between the first and second control gates. The NAND string also includes a blocking dielectric located adjacent the plurality of control gate electrodes, at least one charge storage region located adjacent the blocking dielectric and a tunnel dielectric located between the at least one charge storage region and the semiconductor channel. At least one of the semiconductor channel, blocking dielectric or tunnel dielectric is doped with fluorine. Another embodiment relates to a method of making a monolithic three dimensional NAND string comprising forming a stack of alternating layers of a first material and a second material different from the first material over a substrate, forming an at least one front side opening in the stack and forming at least a portion of a memory film in the at least one front side opening. The method also includes forming a semiconductor channel in the at least one front side opening and doping at least one of the memory film and the semiconductor channel with fluorine in-situ during deposition or by annealing in a fluorine containing atmosphere. Short term and long term data retention are useful parameters for NAND string memory devices. The inventors have realized that short term and long term data retention can be improved by doping one or more of the semiconductor channel, blocking dielectric or tunnel dielectric with fluorine. Fluorine passivates defects, such as dangling bonds and electronic traps located at both the interface between layers and inside the layers. Passivation of the tunnel dielectric and the blocking dielectric reduces charge leakage through these layers, resulting in better data retention and endurance. Passivation of the channel improves the channel quality, resulting in improved cell current and cell performance. As discussed in more detail below, in an embodiment, the concentration of fluorine atoms can be in the range of 1×1017 to 1×1021 cm3. In an alternative embodiment, the fluorine concentration may be in the range of 0.1-5 atomic percent (at %). As discussed in more detail below, the tunnel dielectric may be a dielectric film that includes a layer of silicon nitride or silicon oxynitride between a first layer of silicon oxide and a second layer of silicon oxide. Either the first layer of silicon oxide, the second layer of silicon oxide, both the first and second layers of silicon oxide are doped with fluorine. Additionally, the blocking dielectric may be a dielectric film that includes a layer of a metal oxide, such as Al2O3 and a layer of silicon oxide. Either the layer of Al2O3, the layer of silicon oxide or both the layer of Al2O3 and the layer of silicon oxide may be doped with fluorine. A monolithic three dimensional memory array is one in which multiple memory levels are formed above a single substrate, such as a semiconductor wafer, with no intervening substrates. The term “monolithic” means that layers of each level of the array are directly deposited on the layers of each underlying level of the array. In contrast, two dimensional arrays may be formed separately and then packaged together to form a non-monolithic memory device. For example, non-monolithic stacked memories have been constructed by forming memory levels on separate substrates and adhering the memory levels atop each other, as in Leedy, U.S. Pat. No. 5,915,167, titled “Three Dimensional Structure Memory.” The substrates may be thinned or removed from the memory levels before bonding, but as the memory levels are initially formed over separate substrates, such memories are not true monolithic three dimensional memory arrays. In some embodiments, the monolithic three dimensional NAND string 150 comprises a semiconductor channel 1 having at least one end portion extending substantially perpendicular to a major surface 100 Alternatively, the semiconductor channel 1 may have a U-shaped pipe shape, as shown in In some embodiments, the semiconductor channel 1 may be a filled feature, as shown in A first source electrode 102 Each NAND string 150 contains a NAND memory cell region in the memory device levels 70 which includes the semiconductor channel 1 which contains a portion la which extends substantially perpendicular to the major surface 100 The device contains a plurality of control gate electrodes 3 that extend substantially parallel to the major surface 100 Furthermore, each NAND string 150 contains at least one memory film 13 which is located adjacent to the semiconductor channel 1 (e.g., at least next to portion 1 As shown in The substrate 100 can be any semiconducting substrate known in the art, such as monocrystalline silicon, IV-IV compounds such as silicon-germanium or silicon-germanium-carbon, III-V compounds, II-VI compounds, epitaxial layers over such substrates, or any other semiconducting or non-semiconducting material, such as silicon oxide, glass, plastic, metal or ceramic substrate. The substrate 100 may include integrated circuits fabricated thereon, such as driver circuits for a memory device. Any suitable semiconductor materials can be used for semiconductor channel 1, for example silicon, germanium, silicon germanium, or other compound semiconductor materials, such as III-V, II-VI, or conductive or semiconductive oxides, etc. The semiconductor material may be amorphous, polycrystalline or single crystal. The semiconductor channel material may be formed by any suitable deposition methods. For example, in one embodiment, the semiconductor channel material is deposited by low pressure chemical vapor deposition (LPCVD). In some other embodiments, the semiconductor channel material may be a recrystallized polycrystalline semiconductor material formed by recrystallizing an initially deposited amorphous semiconductor material. The insulating fill material 2 may comprise any electrically insulating material, such as silicon oxide, silicon nitride, silicon oxynitride, or other high-k insulating materials. The monolithic three dimensional NAND string further comprise a plurality of control gate electrodes 3, as shown in A blocking dielectric 7 is located adjacent to the control gate(s) 3 and may surround the control gate electrodes 3, as shown in The monolithic three dimensional NAND string also comprise a charge storage region 9. The charge storage region 9 may comprise one or more continuous layers which extend the entire length of the memory cell portion of the NAND string, as shown in Alternatively, the charge storage region may comprise a plurality of discrete charge storage regions 9, as shown in The tunnel dielectric 11 of the monolithic three dimensional NAND string is located between charge storage region 9 and the semiconductor channel 1. The blocking dielectric 7 and the tunnel dielectric 11 may be independently selected from any one or more same or different electrically insulating materials, such as silicon oxide, silicon nitride, silicon oxynitride, or other insulating materials. The blocking dielectric 7 and/or the tunnel dielectric 11 may include multiple layers of silicon oxide, silicon nitride and/or silicon oxynitride (e.g., ONO layers) or high-k materials such as aluminum oxide, hafnium oxide or combinations thereof. The blocking dielectric 7, charge storage region(s) 9 and the tunnel dielectric 11 together is also referred to herein as a memory film 13, as shown in If desired, an optional barrier layer 4 may be located between the control gate electrode 3 and the blocking dielectric 7, as shown in In the embodiment illustrated in 6A, the blocking dielectric 7 comprises a first blocking dielectric 71 and a second blocking dielectric 72. In an embodiment, the first blocking dielectric 71 comprises a metal oxide layer, such as an Al2O3 layer and the second blocking dielectric 72 comprises a silicon oxide (e.g., SiO2) layer. The first blocking dielectric 71 is located adjacent to the control gate electrodes 3 and the second blocking dielectric 72 is located adjacent to the charge storage region 9. In an embodiment, the charge storage region 9 comprises a charge trapping material, such as silicon nitride. In an embodiment, the tunnel dielectric 11 comprises a tunnel dielectric film comprising a silicon nitride (e.g., Si3N4) or silicon oxynitride (SiON) layer 112 located between a first silicon oxide (e.g., SiO2) layer 111 and a second silicon oxide (e.g., SiO2) layer 113. The semiconductor channel 1 is formed over the tunnel dielectric 11, as illustrated in In an embodiment, at least one of the semiconductor channel 1, blocking dielectric 7 or tunnel dielectric 11 is doped with fluorine. In an embodiment, the semiconductor channel 1, the blocking dielectric 7 and the tunnel dielectric 11 are doped with fluorine. In an embodiment, the blocking dielectric 7 comprises a first blocking dielectric 71 comprising the Al2O3 layer doped with fluorine and a second blocking dielectric 72 comprising a silicon oxide layer doped with fluorine. Alternatively, either the first blocking dielectric 71 or the second blocking dielectric 72 is doped with fluorine. In an embodiment, the tunnel dielectric 11 comprises a dielectric film as described above and either the first silicon dioxide layer 111 or the second silicon dioxide 113 layer is doped with fluorine. In another embodiment, the tunnel dielectric 11 comprises a dielectric film as described above and both the first silicon dioxide layer 111 and the second silicon dioxide 113 layer are doped with fluorine. In an embodiment, at least one of the semiconductor channel 1, blocking dielectric 7 or tunnel dielectric 11 is formed in an atmosphere comprising fluorine. In an embodiment, the tunnel dielectric 11 (e.g., layer 113) may be formed by an in-situ steam generated (ISSG) process. In this process, the atmosphere may comprise, but is not limited to, one or more of fluorine containing precursor vapors, such as hydrofluoric acid, fluorosilicic acid or difluorosilane, in addition to the steam generated from hydrogen and oxygen precursors. In an alternative embodiment of the method, the tunnel dielectric 11 may be formed be plasma enhanced chemical vapor deposition (PEVCD) at 350-450° C. using an atmosphere including tetraethoxysilane (TEOS), O2 and a fluorine containing gas, such as C2F6. Alternatively, the tunnel dielectric 11 may be formed by atomic layer deposition (ALD) at 400-500° C. in an atmosphere including a fluorine containing gas, such as C2F6. The blocking dielectric 7 and the channel 1 may be formed with similar processing as the tunnel dielectric. In an embodiment, the tunnel dielectric 11, blocking dielectric 7 and/or the semiconductor channel 1 are doped with fluorine during formation (i.e. in-situ). Alternatively, the tunnel dielectric 11, blocking dielectric 7 and/or semiconductor channel 1 may be formed essentially fluorine free and doped with fluorine after formation. In this embodiment, the tunnel dielectric 11, blocking dielectric 7 and/or semiconductor channel 1 is exposed to a fluorine containing atmosphere 300 (e.g. C2F6 ambient or CF4 plasma) and then one or more annealing steps performed to diffuse the fluorine dopant into the tunnel dielectric 11, blocking dielectric 7 and/or the semiconductor channel 1. In an embodiment, the fluorine concentration is in a range of 0.1 at %-5 at %. In an alternative embodiment, the fluorine concentration is in a range of 1×1017-1×1021 cm−3. In other embodiments, the fluorine concentrations, in terms of atomic percentage or atomic concentration per unit volume can be higher or lower. In a first embodiment of making monolithic three dimensional NAND strings 150, a stack 120 of alternating first material layers 19 and second material layers 121 is provided over a major surface 100 If desired, a top insulating layer 19 The next step includes forming at least a portion of the memory film 13 in the front side openings 81. For example, the tunnel dielectric 11 is formed in the front side opening 81. If desired, the blocking dielectric 7 and/or the charge storage region(s) 9 portions of the memory film 13 may also be formed in the front side openings 81 prior to forming the tunnel dielectric 11, such that the entire memory film 13 is formed in the front side openings 81. Thus, in this embodiment, the method include forming the blocking dielectric layer 7 in the front side openings 81, forming the at least one charge storage region 9 over the blocking dielectric layer 7 in the front side openings, and forming the tunnel dielectric layer 11 over the at least one charge storage region 9 in the front side openings. A semiconductor channel 1, the optional core dielectric 2 and the drain region 103 In an embodiment, forming at least a portion of a memory film 13 in the front side opening 81 comprises forming a first blocking dielectric 71 comprising Al2O3 in-situ doped with fluorine in the front side opening and further comprising forming a second blocking dielectric 72 comprising silicon oxide in-situ doped with fluorine in either the front side opening 81 or in the back side recesses 182 through the back side opening 84 prior to forming the control gate electrodes 3. In an embodiment, the first layer 111 of silicon oxide of the tunnel dielectric 11 is located adjacent to the charge storage region 9 and the first layer 111 of silicon oxide is formed by either PECVD using TEOS, O2 and C2F6 sources, or by ALD using a silicon containing precursor, an oxygen precursor and C2F6 sourced to form an in-situ doped first layer 111 of silicon oxide. In an embodiment, the second layer 113 of silicon oxide is located adjacent to the semiconductor channel 1 and the second layer 113 of silicon oxide is formed by either PECVD using TEOS, O2 and C2F6 sources to form an in-situ doped second layer 113 of silicon oxide or by in-situ steam generation (ISSG) oxidation of a portion of the layer 112 of silicon nitride or silicon oxynitride in an ambient containing steam and at least one of hydrofluoric acid, fluoro silicic acid or difluorosilane. In an embodiment, at least one of the channel 1, blocking dielectric 7 and/or the tunnel dielectric 11 are doped with fluorine by annealing in a CF4 plasma after deposition. In an embodiment, the semiconductor channel comprises an amorphous silicon or polysilicon channel which is doped in-situ with fluorine or doped with fluorine by annealing in a CF4 plasma after deposition. Then, at least a portion of the sacrificial second material layers 121 are removed through the back side openings 84 to form back side recesses 182 between the first material layers 19, as shown in Alternatively, the blocking dielectric 7 may be formed from the back side in the back side recesses 182 prior to the control gate electrodes 3. In this embodiment, forming the blocking dielectric layer comprises forming the blocking dielectric layer in the back side opening 84 and in the back side recesses 182. If desired, the at least one charge storage region 9 may be formed through either the front side opening or the back side opening. Thus, the step of forming the at least one charge storage region 9 comprises at least one of forming the at least one charge storage region 9 prior to forming the blocking dielectric in the back side opening 84 or forming the at least one charge storage region 9 over the blocking dielectric 7 in the front side opening 81 or over the sidewall in the front side opening 81 (if the blocking dielectric is formed through the back side opening). Metal or metal alloy control gate electrodes 3 are then formed in the back side recesses 182 through the back side openings 84, as shown in Then, as shown in The insulating layer 205, such as a silicon oxide layer, is formed on sidewalls and bottom of the back side trenches 84, as shown in The source electrode 102 is then formed in the back side trench 84 in contact with the source region in the p-well 110 in the substrate 100, as shown in Although the foregoing refers to particular preferred embodiments, it will be understood that the invention is not so limited. It will occur to those of ordinary skill in the art that various modifications may be made to the disclosed embodiments and that such modifications are intended to be within the scope of the invention. All of the publications, patent applications and patents cited herein are incorporated herein by reference in their entirety. A method of making a monolithic three dimensional NAND string comprising forming a stack of alternating layers of a first material and a second material different from the first material over a substrate, forming an at least one front side opening in the stack and forming at least a portion of a memory film in the at least one front side opening. The method also includes forming a semiconductor channel in the at least one front side opening and doping at least one of the memory film and the semiconductor channel with fluorine in-situ during deposition or by annealing in a fluorine containing atmosphere. 1. A monolithic three dimensional NAND string, comprising:
a semiconductor channel, at least one end part of the semiconductor channel extending substantially perpendicular to a major surface of a substrate; a plurality of control gate electrodes extending substantially parallel to the major surface of the substrate, wherein the plurality of control gate electrodes comprise at least a first control gate electrode located in a first device level and a second control gate electrode located in a second device level located over the major surface of the substrate and below the first device level, wherein the first control gate electrode is separated from the second control gate electrode by an insulating layer located between the first and second control gates; a blocking dielectric located adjacent the plurality of control gate electrodes; at least one charge storage region located adjacent the blocking dielectric; and a tunnel dielectric located between the at least one charge storage region and the semiconductor channel, wherein at least one of the semiconductor channel, blocking dielectric or tunnel dielectric is doped with fluorine. 2. The monolithic three dimensional NAND string of 3. The monolithic three dimensional NAND string of 4. The monolithic three dimensional NAND string of 5. The monolithic three dimensional NAND string of 6. The monolithic three dimensional NAND string of 7. The monolithic three dimensional NAND string of 8. The monolithic three dimensional NAND string of 9. The monolithic three dimensional NAND string of 10. The monolithic three dimensional NAND string of 11. The monolithic three dimensional NAND string of 12. The monolithic three dimensional NAND string of the substrate comprises a silicon substrate; the monolithic three dimensional NAND string is located in an array of monolithic three dimensional NAND strings over the silicon substrate; at least one memory cell in the first device level of the three dimensional array of NAND strings is located over another memory cell in the second device level of the three dimensional array of NAND strings; and the silicon substrate contains an integrated circuit comprising a driver circuit for the memory device located thereon. 13. A method of making a monolithic three dimensional NAND string, comprising:
forming a stack of alternating layers of a first material and a second material different from the first material over a substrate; forming an at least one front side opening in the stack; forming at least a portion of a memory film in the at least one front side opening; forming a semiconductor channel in the at least one front side opening; and doping at least one of the memory film and the semiconductor channel with fluorine in-situ during deposition or by annealing in a fluorine containing atmosphere. 14. The method 15. The method 13, wherein the memory film comprises a blocking dielectric, a tunnel dielectric and at least one charge storage region located between the blocking dielectric and the tunnel dielectric. 16. The method of 17. The method of 18. The method of 19. The method of 20. The method of 21. The method of 22. The method of 23. The method of 24. The method of 25. The method of 26. The method of 27. The method of 28. The method of FIELD
BACKGROUND
SUMMARY
BRIEF DESCRIPTION OF THE DRAWINGS
DETAILED DESCRIPTION













