WO2007067604A2 - Procede de fabrication de films de chalcogenure dopees, alliees et non dopees par depot chimique metal oxyde en phase vapeur - Google Patents
Procede de fabrication de films de chalcogenure dopees, alliees et non dopees par depot chimique metal oxyde en phase vapeur Download PDFInfo
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- WO2007067604A2 WO2007067604A2 PCT/US2006/046524 US2006046524W WO2007067604A2 WO 2007067604 A2 WO2007067604 A2 WO 2007067604A2 US 2006046524 W US2006046524 W US 2006046524W WO 2007067604 A2 WO2007067604 A2 WO 2007067604A2
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 229910000618 GeSbTe Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 35
- 238000000151 deposition Methods 0.000 claims description 33
- 229910052714 tellurium Inorganic materials 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 29
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052787 antimony Inorganic materials 0.000 claims description 25
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- 239000012159 carrier gas Substances 0.000 claims description 17
- 229910000078 germane Inorganic materials 0.000 claims description 14
- 238000005275 alloying Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011669 selenium Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- PORFVJURJXKREL-UHFFFAOYSA-N trimethylstibine Chemical compound C[Sb](C)C PORFVJURJXKREL-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052798 chalcogen Inorganic materials 0.000 claims description 9
- 150000001787 chalcogens Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- NYOZTOCADHXMEV-UHFFFAOYSA-N 2-propan-2-yltellanylpropane Chemical compound CC(C)[Te]C(C)C NYOZTOCADHXMEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- REWNSVPMLJDJCQ-UHFFFAOYSA-N diethylgermane Chemical compound CC[GeH2]CC REWNSVPMLJDJCQ-UHFFFAOYSA-N 0.000 claims description 4
- AEOGRWUNSVGMMJ-UHFFFAOYSA-N trimethylgermane Chemical compound C[GeH](C)C AEOGRWUNSVGMMJ-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052986 germanium hydride Inorganic materials 0.000 claims description 3
- QQXSEZVCKAEYQJ-UHFFFAOYSA-N tetraethylgermanium Chemical compound CC[Ge](CC)(CC)CC QQXSEZVCKAEYQJ-UHFFFAOYSA-N 0.000 claims description 3
- KKOFCVMVBJXDFP-UHFFFAOYSA-N triethylstibane Chemical compound CC[Sb](CC)CC KKOFCVMVBJXDFP-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000012705 liquid precursor Substances 0.000 claims 9
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000012782 phase change material Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 48
- 230000015654 memory Effects 0.000 description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 19
- 239000010409 thin film Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 9
- 238000004876 x-ray fluorescence Methods 0.000 description 9
- 229910018321 SbTe Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910005872 GeSb Inorganic materials 0.000 description 4
- 229910005900 GeTe Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- DDJAGKOCVFYQOV-UHFFFAOYSA-N tellanylideneantimony Chemical compound [Te]=[Sb] DDJAGKOCVFYQOV-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
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- 238000011165 process development Methods 0.000 description 2
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- 238000002310 reflectometry Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- LQIKDUWYQKLRNS-UHFFFAOYSA-N 2-propan-2-ylselanylpropane Chemical compound CC(C)[Se]C(C)C LQIKDUWYQKLRNS-UHFFFAOYSA-N 0.000 description 1
- 229910000763 AgInSbTe Inorganic materials 0.000 description 1
- 102000001690 Factor VIII Human genes 0.000 description 1
- 108010054218 Factor VIII Proteins 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910005865 GeSbTeSe Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- CBJZJSBVCUZYMQ-UHFFFAOYSA-N antimony germanium Chemical compound [Ge].[Sb] CBJZJSBVCUZYMQ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VDDXNVZUVZULMR-UHFFFAOYSA-N germanium tellurium Chemical compound [Ge].[Te] VDDXNVZUVZULMR-UHFFFAOYSA-N 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
- H10N70/023—Formation of switching materials, e.g. deposition of layers by chemical vapor deposition, e.g. MOCVD, ALD
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8828—Tellurides, e.g. GeSbTe
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
Definitions
- This invention relates to a Method of Making Undoped, Alloyed and Doped
- Flash memory chips are Flash memory chips, so-called because of the ability to write them individually while erasing them in chunks. This type of device is ubiquitous in today's cell phones, digital cameras, media cards etc.
- Flash memory suffers from several shortcomings that limit their market potential. Primarily, writing data to a Flash memory is too slow for Flash to rival its DRAM cousins.
- Flash memories can only be reprogrammed a limited number of times without incurring wear-out, typically on the order of a million re-programming cycles. While this may be enough for certain applications, it makes Flash memory ill-suited for general computing applications.
- FRAM Ferroelectric RAM
- MRAM Magnetoresistive RAM
- C-RAM Chalcogenide RAM
- OFUM Ovonic Unified Memory
- PRAM Phase-Change RAM
- C-RAM apart from having a small cell size and large endurance, is a low-power memory. Since the binary information is represented by two different phases of the material it is inherently nonvolatile, requiring no energy to keep the material in either of its two stable binary structural states. In addition, since the data in a chalcogenide memory element is stored as a structural phase rather than an electrical charge or state, it is expected to be impervious to ionizing radiation effects. This makes C-RAM ideally suited for space-based and military applications.
- Nonvolatile memory devices are found in the majority of military as well as commercial systems.
- the type of nonvolatile memory of this program, C-RAM is especially relevant to Military Device Applications (MDA) for its radiation hardness.
- MDA Military Device Applications
- C-RAM is inherently resistant to radiation, making this device an attractive option for military and aerospace applications.
- C-RAM memory devices can be operated at low voltages and offer fast write/erase speeds.
- the ease with which C-RAM memory can be scaled to smaller sizes offers the opportunity to develop high density memories that are radiation hardened.
- phase-change nonvolatile memories are focused on the chalcogenide material Ge 2 Sb 2 Te 5 used for rewriteable optical media (CD-RW and DVD-RW).
- chalcogen refers to the Group VI elements of the periodic table (among them sulfur (S), selenium (Se) and tellurium (Te)).
- Chalcogenide refers to compounds or alloys, hereafter referred to as alloys, containing at least one of these elements such as the alloy of germanium, antimony, and tellurium discussed here. This phase-change technology uses a thermally activated, rapid, reversible change in the structure of the alloy to store data.
- the two structural states of the chalcogenide alloy are an amorphous state and a polycrystalline state. Relative to the amorphous state, the polycrystalline state shows a dramatic increase in free electron density, similar to a metal. This difference in free electron density gives rise to a difference in reflectivity and resistivity.
- a laser is used to heat the material to change states. The state of the memory is read by directing a low-power laser at the material and detecting the difference in reflectivity between the two phases.
- a memory cell consists of a top electrode, a layer of chalcogenide and a bottom electrode that at the base is connected to a transistor (see Figure 1 which is a simplified diagram of a chalcogenide memory cell taken from J. Maimon, K. Hunt, L. Burcin, J. Rodgers, K. Knowles, "Integration And Circuit Demonstration of
- Chalcogenide Memory Elements with a Radiation Hardened CMOS Technology Proceedings 2002 Non-Volatile Memory Technology Symposium, paper no. 23, Nov. 2002. Reading the cell is done by measuring the resistance. Resistive heating is used to change the phase of the chalcogenide layer. To write data into the cell, the chalcogenide is heated past its melting point (Tm) and then rapidly cooled to make it amorphous. To make it crystalline, it is heated just below its melting point and held there for approximately 50 ns, giving the atoms time to position themselves in their crystal locations.
- Tm melting point
- C-RAM Complementary Metal-organic chemical vapor deposition
- Single cells have been studied in detail with reported cycling endurance up to one trillion and write/erase speeds in the tens of nanoseconds. Cycling endurance is observed to be dependent on the magnitude of the reset current. Overheating the cell with a large programming current causes failed cells to get stuck at low resistance states.
- Programming currents are typically on the order of 1 mA, but for practical reasons are desirable to be reduced to 0.2 mA to 0.4 m A.
- One way to achieve this is to dope the chalcogenide material with nitrogen. Nitrogen-doped chalcogenides such as Ge 2 Sb 2 Te S have a higher resistance and therefore a lower programming current. Similarly, alloying the chalcogenide with Sn or Se may have the same effect on programming current.
- C-RAM devices are currently produced using sputtering.
- sputtering limits further device improvements because of difficulties in meeting device architecture / conformality requirements for increased endurance, reliability and higher density components.
- sputtering has limited flexibility in varying the composition of the chalcogenide alloy. MOCVD overcomes these and other sputter related limitations.
- C-RAM is a phase change memory that stores its digital information as either a crystalline or amorphous structural phase identified through distinctly different resistive paths to conductive charge in a thin, chalcogenide layer. This mechanism of data storage offers an important advantage over other types of memory, such as
- the active, chalcogenide layer is fabricated by sputtering. This process has several characteristics that limit device performance and its technological advancement as implemented in nonvolatile device structures. Specifically, practical endurance (the number of programming cycles before failure) of sputter-made C-RAMs is ⁇ 10 8 . Furthermore, improved conformality will lead to higher speeds and lower operating voltage through increased density scaling.
- MOCVD Metalorganic Chemical Vapor Deposition is a well-established manufacturing technology that has a demonstrated capability of uniformly fabricating thin films of high quality and excellent conformality integrated circuit device layers at a high throughput rate.
- MOCVD also offers the opportunity to easily vary the alloy composition of the chalcogenide layer which should further improve endurance and other device characteristics.
- MOCVD has an advantage over sputtering for alloy/dopant tuning in that it offers run-to-run tuning of composition through flow control as compared to the need to purchase new targets and to re-setup and qualify the tool for sputtering; thus greatly speeding the process and reducing the cost.
- the present invention is directed to an improved production technology for chalcogenide-based nonvolatile memories (C-RAM) based on Metal-Organic Chemical Vapor Deposition (MOCVD).
- C-RAM chalcogenide-based nonvolatile memories
- MOCVD Metal-Organic Chemical Vapor Deposition
- Figure 4 shows a microscopic image of a representative GeSbTe thin film fabricated by MOCVD as part of this work.
- the film was fabricated in accordance with processes described herein.
- the film was conclusively verified to contain all three elements by both X-Ray Fluorescence (XRF) and Auger Electron Spectroscopy (AES).
- XRF X-Ray Fluorescence
- AES Auger Electron Spectroscopy
- GeSbTe-based thin films were fabricated by MOCVD in both single layer fashion, i.e. simultaneous feeding of all precursors into the chamber, and multilayer fashion, i.e. alternately, germanium (Ge) and antimony/tellurium
- the fabricated films were characterized by X-Ray Fluorescence (XRF) and Auger Electron Spectroscopy (AES) and were conclusively found to contain all three constituent elements.
- XRF X-Ray Fluorescence
- AES Auger Electron Spectroscopy
- Germane (GeH 4 ) gas was used as the germanium precursor.
- metalorganic germanium sources such as tetraethylgermane (C 2 Hs) 4 Ge, diethylgermane (C 2 Hs) 2 GeH 2 , and trimethylgermane (CHs) 3 GeH can be used in the present process, they were found to be more or less effective than
- TMSb Trimethylantimony
- C 2 Hs Triethylantimony
- TESb Triethylantimony
- C 3 H 7 Diisopropyltelluride
- Te Triethylantimony
- the temperature at which deposition takes place ranges from 450 0 C to 500 0 C.
- the chamber pressure at which deposition takes places ranges from 5 Torr to 10 Torr (although other chamber pressures may be utilized).
- Figure 1 depicts a chalcogenide-based memory cell
- Figure 2 schematic representation of a CVD deposition system suitable for carrying out the present invention
- Figure 3 shows the XRF spectrum for a representative GeSbTe deposition done in accordance with the present invention.
- Figure 4 is a photomicrograph of a GeSbTe film deposited done in accordance with the present invention.
- Figure 2 depicts the first of two CVD chambers that were used in this work. Gases are fed into a vacuum reactor chamber 20 through a showerhead located inside chamber 20 which contains gas inlets 22 for precursor vapors and a carrier gas 24, which in this case is hydrogen. Heating of chamber 20 is achieved through resistive heating of SiC-coated graphite filaments. The chamber pressure is recorded through a baratron. The temperature of chamber 20 is recorded via thermocouples that are positioned in close proximity to the substrate platter. Wafers are mounted on a substrate platter that is equipped with a ferrofluidic rotation assembly rotated by an external motor 26. During deposition the entire wafer assembly rotates at a predetermined speed, typically 750 revolutions per minute.
- Chamber 20 is equipped with hardware for 6" wafer processing through an automated wafer transfer robot and load lock chamber (not shown).
- Figure 2 also depicts a schematic of the gas panel used for depositing GeSbTe- based films.
- a germane gas bottle 28 and hydrogen gas bottle 24 are shown that tie into the main gas panel.
- Three bubbler sources 3Oa 5 30b and 30c are depicted in the center of the drawing, one for the antimony precursor, one for the tellurium precursor and a spare one that can be used for metalorganic germanium, or doping/alloying precursors if so desired.
- Bubbler sources 3Oa 5 30b and 30c are each surrounded by liquid baths 32a, 32b and 32c to maintain the precursors at the desired temperatures
- the precursor vapors are transported to the showerhead by the carrier gas bubbled therethrough, from where they are fed into the chamber through needle valves 34.
- the lower right portion of the drawing represents the vaccum pumping manifold 36.
- the reactor is comprised of a vertically mounted IV2" diameter quartz tube.
- the top flange was equipped with a gas feedthrough. Precursor and carrier gas mix immediately before entering the reactor.
- a baratron was mounted on the top flange for pressure control.
- a small graphite cylinder is used as a sample holder. Heating of the small reactor is achieved through 500 W quartz halogen light bulbs. This type of light bulb provides a rapid heating up and cooling down cycle of the chamber, thereby considerably reducing the time needed per process run.
- Germanium film was deposited on a 6" silicon wafer using the large MOCVD reactor shown in Fig. 2.
- the film was grown at a temperature of 540 0 C for 30 minutes at a 3 Torr chamber pressure.
- the average thickness of the film was found to be 640 A.
- the deposition of Germanium was routinely achieved in both the large reactor as well as the small quartz reactor.
- the source of the germanium was germane gas, hydrogen was the carrier gas and Diisopropyltelluride (C 3 H- Z ) 2 Te [DiPTe] was used as the tellurium precursor.
- the XRF spectrum for a representative GeTe deposition indicates that both germanium and tellurium are present in the film, albeit at a low tellurium concentration. The film appeared polycrystalline upon deposition.
- the source of the germanium was germane gas, hydrogen was the carrier gas and Trimethylantimony (CHa) 3 Sb [TMSb] was used as the antimony precursor XRF analysis showed the presence of germanium and antimony in the deposited film.
- the XRF spectrum of the antimony-tellurium film (SbTe) shows the presence of tellurium in the film.
- Auger Electron Spectroscopy (AES) was performed on the sample.
- Sputter depth profiles were acquired from the sample. Carbon, oxygen, antimony, and tellurium were monitored as a function of sputter depth. The profiles were quantified using elemental sensitivity factors.
- the depth scale was calibrated using a thermal oxide of silicon of known thickness and assuming that these materials sputter at the same rate as SiO 2 -
- both antimony and tellurium were recorded as well as atomic oxygen and carbon.
- the profile obtained from the described sample shows that the coating is of uniform composition to the final sputter depth.
- the atomic concentrations of Sb (40%) and Te (60%) prove the film to be a compositionally correct Sb 2 Te 3 chalcogenide.
- Initial GeSbTe films were grown in a single layer fashion, i.e. all precursors were simultaneously fed into the chamber. Exemplary fabrication details are listed in Table E.
- the starting precursor concentration By varying the starting precursor concentration, the resulting film composition can be controlled.
- additional precursors such as Tin (Sn), selenium (Se), Silicon (Si), nitrogen (N) and gallium (Ga)
- the GeSbTe- based thin film composition can be alloyed/doped.
- Example precursors for Sn, Se 5 Si, N, and Ga are tetraethyltin ((C 2 Hs) 4 Sn) 3 di-isopropyl selenium ((C 3 H- ⁇ ) 2 Se), silane (SiH 4 ), ammonia (NH 3 ), and trimethyl gallium ((CH 3 ) 3 Ga), respectively.
- Auger Electron Spectroscopy was also performed on a representative GeSbTe film. Again a sputter depth profiles was acquired from the sample. Carbon, oxygen, germanium, antimony, and tellurium were monitored as a function of sputter depth. The profiles were quantified using elemental sensitivity factors. The depth scale was calibrated using a thermal oxide of silicon of known thickness and assuming that these materials sputter at the same rate as SiO 2 . The profile for the sample was acquired from a relatively smooth area of the sample. The depth profile shows the presence of a germanium-rich oxide followed by a layer containing Ge, Sb 3 Te, and O. Silicon was detected after sputtering ⁇ 8O ⁇ A.
- the secondary electron images showed that much of the wafer still contained coating material after the completion of the profile. Therefore a second profile was started on one of these remaining regions.
- the second profile showed the coating in this area had a uniform composition of Sb (30%), Ge (10%), and Te (60%) to a depth of ⁇ l,500A .
- the films were generally found to have a large surface roughness. Further efforts were made to reduce the roughness of the deposited films through process improvements. One improvement in particular, was the use of diethylgermane as a germanium precursor which was found to improve the surface roughness significantly compared to films prepared using germane, when growing in one step. The result of this effort is depicted in Figure 4 This figure shows a microscopic image (magnification 150Ox) of a GeSbTe film. Upon visual inspection, the film was found to be smooth. Microscopy revealed that the film is of a polycrystalline nature with large grains (several microns in diameter) as evidenced by the grain boundaries. In addition, the XRF spectrum is shown, indicating that all three elements are present. Other films appeared amorphous and yet others very rough depending upon process parameters.
- the present process is not in any way limited to the direct deposition of the material directly onto a substrate.
- the deposition of the material is not in any way limited to the direct deposition of the material directly onto a substrate.
- chalcogenide material may be part of a multiple step process for forming an integrated circuit, such as the memory chip shown in Fig. 1 herein.
- the chalcogenide film can be located in between a top and a bottom layer, either of which may consist of a metal, carbon, highly doped semiconductor, among others.
- the properties of the deposited film can be controlled by varying the process parameters such as precursor composition, temperature, time, pressure, and flow rate of the precursors and carrier gases.
- Additional precursors may also be added to the deposition process so as to add a doping/alloying element to the deposited film suitable doping/alloying elements include: N, Ga, Si, Ni 5 V, Se, S, and Sn, among others. Whether the element is a dopant or an alloy depends on the nature of the added element and the amount added.
- dopant refers to a substitution of an element by a small amount of an element of a different valence (or group in the periodic table), for example substituting N (group V, nominal valence -3) for Se (group VI, nominal valence -2), whereas alloy refers to an addition of any proportion of an element generally of the same valence or group in the periodic table, for example Si (group IV) substituted for Ge (group IV), or in reference to a solid solution of metals. .
- the present process may also be used to manufacture other
- chalcogenide films such as AgInSbTe (which also has phase- properties), InSe, SbSe, SbTe, InSbSe, InSbTe, GeSbSe, and GeSbTeSe.
- GeSbTe-based thin films were fabricated by MOCVD in both single layer fashion, i.e. simultaneous feeding of all precursors into the chamber, and multilayer fashion, i.e. alternately, germanium (Ge) and antimony/tellurium
- the fabricated films were characterized by X-Ray Fluorescence (XRF) and Auger Electron Spectroscopy (AES) (surface and depth profile) and were conclusively found to contain all three constituent elements.
- XRF X-Ray Fluorescence
- AES Auger Electron Spectroscopy
- Germane (GeHU) gas was used as the germanium precursor.
- metalorganic germanium sources such as tetraethylgermane (C 2 Hs) 4 Ge, diethylgermane (C 2 Hs) 2 GeH 2 , and trimethylgermane (CHj) 3 GeH can be used in the present process as they were found to be more or less effective than Germane and can impede deposition under certain circumstances.
- Diisopropyltelluride (C 3 Hv) 2 Te was used as the tellurium precursor.
- the temperature at which deposition takes place ranges from 450 0 C to 500 0 C.
- the chamber pressure at which deposition takes places ranges from 5 Torr to 10 Torr.
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Abstract
L'invention concerne un procédé de fabrication de pellicules de chalcogénure dopées, alliées et non dopées par dépôt chimique en phase vapeur et en particulier un film de GeSbTe qui est un matériau à changement de phase. Ces films sont utiles dans des dispositifs à mémoire électronique et dans d'autres applications. Selon le procédé de l'invention, les précurseurs en phase gazeuse ou vapeur des éléments sont transportés jusqu'à une chambre de réaction où ils sont déposés sur un substrat chauffé dans des conditions régulées.
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Cited By (17)
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WO2009039187A1 (fr) * | 2007-09-17 | 2009-03-26 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Précurseurs de tellure pour le dépôt d'un film gst |
WO2009051799A1 (fr) * | 2007-10-18 | 2009-04-23 | Structured Materials Inc. | Composés sulfure de germanium pour éléments de mémoire à électrolyte solide |
US20090285986A1 (en) * | 2008-05-15 | 2009-11-19 | Park Hye-Young | Methods of forming a material layer and methods of fabricating a memory device |
US7749802B2 (en) * | 2007-01-09 | 2010-07-06 | International Business Machines Corporation | Process for chemical vapor deposition of materials with via filling capability and structure formed thereby |
US8093140B2 (en) | 2007-10-31 | 2012-01-10 | Advanced Technology Materials, Inc. | Amorphous Ge/Te deposition process |
US8101237B2 (en) | 2008-05-29 | 2012-01-24 | L'Air Liquide SociétéAnonyme pour I'Etude et I'Exploitation des Procédés Georges Claude | Tellurium precursors for film deposition |
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US8802194B2 (en) | 2008-05-29 | 2014-08-12 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Tellurium precursors for film deposition |
US8834968B2 (en) | 2007-10-11 | 2014-09-16 | Samsung Electronics Co., Ltd. | Method of forming phase change material layer using Ge(II) source, and method of fabricating phase change memory device |
US8852686B2 (en) | 2007-10-11 | 2014-10-07 | Samsung Electronics Co., Ltd. | Method of forming phase change material layer using Ge(II) source, and method of fabricating phase change memory device |
US9240319B2 (en) | 2010-02-03 | 2016-01-19 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Chalcogenide-containing precursors, methods of making, and methods of using the same for thin film deposition |
US9537095B2 (en) | 2008-02-24 | 2017-01-03 | Entegris, Inc. | Tellurium compounds useful for deposition of tellurium containing materials |
CN113969395A (zh) * | 2021-09-14 | 2022-01-25 | 上海交大平湖智能光电研究院 | 一种基于脉冲激光沉积的相变薄膜的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5431738A (en) * | 1991-03-19 | 1995-07-11 | Fujitsu Limited | Apparatus for growing group II-VI mixed compound semiconductor |
US5753936A (en) * | 1978-05-04 | 1998-05-19 | Canon Kabushiki Kaisha | Image forming member for electrophotography |
US6337266B1 (en) * | 1996-07-22 | 2002-01-08 | Micron Technology, Inc. | Small electrode for chalcogenide memories |
US20040168626A1 (en) * | 2001-07-20 | 2004-09-02 | Peter Moeck | Process for forming semiconductor quantum dots with superior structural and phological stability |
US20040231590A1 (en) * | 2003-05-19 | 2004-11-25 | Ovshinsky Stanford R. | Deposition apparatus for the formation of polycrystalline materials on mobile substrates |
-
2006
- 2006-12-06 WO PCT/US2006/046524 patent/WO2007067604A2/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5753936A (en) * | 1978-05-04 | 1998-05-19 | Canon Kabushiki Kaisha | Image forming member for electrophotography |
US5431738A (en) * | 1991-03-19 | 1995-07-11 | Fujitsu Limited | Apparatus for growing group II-VI mixed compound semiconductor |
US6337266B1 (en) * | 1996-07-22 | 2002-01-08 | Micron Technology, Inc. | Small electrode for chalcogenide memories |
US20040168626A1 (en) * | 2001-07-20 | 2004-09-02 | Peter Moeck | Process for forming semiconductor quantum dots with superior structural and phological stability |
US20040231590A1 (en) * | 2003-05-19 | 2004-11-25 | Ovshinsky Stanford R. | Deposition apparatus for the formation of polycrystalline materials on mobile substrates |
Cited By (24)
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US8709863B2 (en) | 2006-11-02 | 2014-04-29 | Advanced Technology Materials, Inc. | Antimony and germanium complexes useful for CVD/ALD of metal thin films |
US8268665B2 (en) | 2006-11-02 | 2012-09-18 | Advanced Technology Materials, Inc. | Antimony and germanium complexes useful for CVD/ALD of metal thin films |
US9219232B2 (en) | 2006-11-02 | 2015-12-22 | Entegris, Inc. | Antimony and germanium complexes useful for CVD/ALD of metal thin films |
US7749802B2 (en) * | 2007-01-09 | 2010-07-06 | International Business Machines Corporation | Process for chemical vapor deposition of materials with via filling capability and structure formed thereby |
WO2009039187A1 (fr) * | 2007-09-17 | 2009-03-26 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Précurseurs de tellure pour le dépôt d'un film gst |
US8454928B2 (en) | 2007-09-17 | 2013-06-04 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Tellurium precursors for GST deposition |
US8852686B2 (en) | 2007-10-11 | 2014-10-07 | Samsung Electronics Co., Ltd. | Method of forming phase change material layer using Ge(II) source, and method of fabricating phase change memory device |
US8834968B2 (en) | 2007-10-11 | 2014-09-16 | Samsung Electronics Co., Ltd. | Method of forming phase change material layer using Ge(II) source, and method of fabricating phase change memory device |
WO2009051799A1 (fr) * | 2007-10-18 | 2009-04-23 | Structured Materials Inc. | Composés sulfure de germanium pour éléments de mémoire à électrolyte solide |
US8093140B2 (en) | 2007-10-31 | 2012-01-10 | Advanced Technology Materials, Inc. | Amorphous Ge/Te deposition process |
US9537095B2 (en) | 2008-02-24 | 2017-01-03 | Entegris, Inc. | Tellurium compounds useful for deposition of tellurium containing materials |
US8703237B2 (en) * | 2008-05-15 | 2014-04-22 | Samsung Electronics Co., Ltd. | Methods of forming a material layer and methods of fabricating a memory device |
KR101489327B1 (ko) * | 2008-05-15 | 2015-02-03 | 삼성전자주식회사 | 물질막의 형성 방법 및 메모리 장치의 제조 방법 |
US20090285986A1 (en) * | 2008-05-15 | 2009-11-19 | Park Hye-Young | Methods of forming a material layer and methods of fabricating a memory device |
US8101237B2 (en) | 2008-05-29 | 2012-01-24 | L'Air Liquide SociétéAnonyme pour I'Etude et I'Exploitation des Procédés Georges Claude | Tellurium precursors for film deposition |
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US9240319B2 (en) | 2010-02-03 | 2016-01-19 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Chalcogenide-containing precursors, methods of making, and methods of using the same for thin film deposition |
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