CN118028779A - Method for preparing gallium oxide film on silicon substrate - Google Patents
Method for preparing gallium oxide film on silicon substrate Download PDFInfo
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- CN118028779A CN118028779A CN202410184869.XA CN202410184869A CN118028779A CN 118028779 A CN118028779 A CN 118028779A CN 202410184869 A CN202410184869 A CN 202410184869A CN 118028779 A CN118028779 A CN 118028779A
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 85
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 61
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 59
- 239000000758 substrate Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 28
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 238000010924 continuous production Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000004377 microelectronic Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000011112 process operation Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 49
- 239000010409 thin film Substances 0.000 description 11
- 230000009471 action Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C23C16/45525—Atomic layer deposition [ALD]
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- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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- 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
- C23C16/40—Oxides
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- 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
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- 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
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- 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
- C23C16/56—After-treatment
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Abstract
The invention relates to a method for preparing a gallium oxide film on a silicon substrate, which belongs to the field of semiconductor material preparation and adopts the following technical scheme: step 1), cleaning a silicon substrate, and placing the cleaned silicon substrate into an atomic layer deposition chamber; step 2), adjusting the vacuum degree in the atomic layer deposition chamber to be less than 1Torr, heating the silicon substrate to 230-280 ℃, and sequentially preparing a hafnium oxide buffer layer and a gallium oxide film layer by adopting a continuous process of an atomic layer deposition method; step 3) adopting high-temperature annealing to obtain a high-quality gallium oxide film on the silicon substrate; the invention adopts continuous process to prepare hafnium oxide buffer layer and gallium oxide film layer on silicon substrate, simplifies process operation flow, avoids surface pollution problem of buffer layer in transfer process, and is beneficial to improving performance of corresponding microelectronic device.
Description
Technical Field
The invention belongs to the field of semiconductor material preparation, and particularly relates to a method for preparing a gallium oxide film on a silicon substrate.
Background
In recent years, ultra-wide band gap semiconductor gallium oxide (Ga 2O3) with excellent physical and chemical properties has attracted extensive attention in the scientific research and industry. The band gap value of gallium oxide is as wide as 4.5-5.1eV, the gallium oxide has breakdown resistance as high as 8MV cm -1, and the Barbary-Gault value for representing the electrical property of the power device is as high as 3214.1, so that the gallium oxide is an excellent material for manufacturing next-generation high-power electronic devices. On the other hand, the light response peak value of gallium oxide directly corresponds to the solar blind ultraviolet band, the absorption coefficient near the absorption edge is as high as 10 5cm-1, and the gallium oxide has great potential application value in the field of photoelectric devices.
The film form is the most compatible structure form of semiconductor material and microelectronic technology, and the gallium oxide film can be used for the channel layer of power device or the light absorption layer of photoelectric device. The preparation of gallium oxide thin films is largely divided into homoepitaxy and heteroepitaxy. Because lattice mismatch and thermal mismatch do not exist, the homoepitaxial gallium oxide film tends to be high in quality, but the current gallium oxide substrate is high in price, the problem of P-type doping cannot be solved, and the method has great limitation in manufacturing electronic devices. The substrate of the heteroepitaxial gallium oxide film mainly comprises sapphire, silicon carbide, silicon and the like. Compared with sapphire and silicon carbide, the silicon material has the advantages of large size, low cost, high thermal conductivity, incomparable integration with silicon-based microelectronic devices and the like as a substrate. However, the silicon and gallium oxide have larger lattice mismatch and thermal mismatch, and the gallium oxide film grown on the silicon substrate has larger stress, is easy to form defects and has cracks on the surface.
The buffer layer process is a common method for optimizing the growth quality of gallium oxide films on silicon substrates. However, two methods or two discontinuous processes are adopted to prepare the buffer layer and the gallium oxide thin film layer respectively at present, and two defects exist in the method. Firstly, the process operation is complex, the buffer layer and the gallium oxide film are intermittent in the preparation process, and even two film growth devices are needed to prepare the buffer layer and the gallium oxide film respectively, so that the time and cost waste is high. Secondly, interface state change can occur in the process of waiting for gallium oxide film preparation after the buffer layer preparation is finished, if a sample needs to be transferred, surface pollution is more easily formed, and the growth quality of the gallium oxide film and the application prospect of corresponding microelectronic devices are affected.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a gallium oxide film on a silicon substrate, which adopts a continuous process to prepare a hafnium oxide buffer layer and a gallium oxide film layer on the silicon substrate, simplifies the process operation flow, avoids the problem of surface pollution of the buffer layer in the transfer process, and is beneficial to improving the performance of corresponding microelectronic devices.
In order to achieve the above purpose, the present invention is realized by the following technical scheme: a method for preparing gallium oxide film on a silicon substrate, which is carried out according to the following method:
step 1), cleaning a silicon substrate, and placing the cleaned silicon substrate into an atomic layer deposition chamber;
Step 2), adjusting the vacuum degree in the atomic layer deposition chamber to be less than 1Torr, heating the silicon substrate to 230-280 ℃, and sequentially preparing a hafnium oxide buffer layer and a gallium oxide film layer by adopting a continuous process of an atomic layer deposition method;
And 3) carrying out high-temperature annealing to obtain the high-quality gallium oxide film on the silicon substrate.
Further, the thickness of the hafnium oxide buffer layer is 30nm to 70nm.
Further, the thickness of the gallium oxide film layer is 50nm to 200nm.
Further, the continuous process of the atomic layer deposition method in the step 2) comprises a hafnium oxide buffer layer with 300-700 cycle periods and a gallium oxide film layer with 1000-4000 cycle periods.
Further, each cycle of the hafnium oxide buffer layer comprises four pulses, a hafnium source pulse using TEMAH as a source, an oxygen source pulse using ozone as a source, and a purge pulse using argon.
Further, each period of the gallium oxide film layer comprises four pulses, a gallium source pulse using TEG or TMG as a source, an oxygen source pulse using ozone as a source, and a purge pulse using argon.
Further, the specific process of high-temperature annealing in the step (3) is as follows: annealing is carried out by an annealing furnace, the annealing atmosphere is nitrogen, the temperature is 900 ℃, and the annealing time is 10min.
Further, the specific steps of cleaning the silicon substrate in the step 1) are as follows: firstly, removing a silicon dioxide layer on the silicon surface by using hydrofluoric acid, and then respectively ultrasonically cleaning for 10 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, the hafnium oxide buffer layer and the gallium oxide thin film layer are prepared on the silicon substrate by setting the technological parameters of the atomic layer deposition method and adopting a continuous process, so that the technological operation flow is simplified, and the problem of surface pollution of the buffer layer in the transfer process is avoided. The buffer layer of hafnium oxide acts to slow down the lattice mismatch and thermal mismatch between silicon and gallium oxide, and can form a high quality gallium oxide film on a silicon substrate, which is beneficial to improving the performance of the corresponding microelectronic device.
2. The invention selects the continuous process of atomic layer deposition method to prepare the buffer layer and the gallium oxide film layer, the process selects hafnium oxide as the buffer layer, and the substrate temperature is controlled in the preparation process to be positioned in the crossing range of the reaction temperature window of the hafnium source and the oxygen source and the reaction temperature window of the gallium source and the oxygen source, so that the temperature does not need to be regulated in the growth process, and the hafnium oxide buffer layer and the gallium oxide film layer can be continuously grown.
3. According to the invention, the hafnium oxide buffer layer and the gallium oxide film layer are prepared by adopting a continuous process of an atomic layer deposition method, and ozone is adopted as an oxygen source in the process, so that the problem that water is used as an oxygen source at low temperature and does not react with gallium sources such as trimethyl gallium or triethyl gallium is avoided, the problem that protective gas needs to be arranged under the condition that plasma oxygen is used as the oxygen source is avoided, the atomic layer deposition procedure is simplified, and the continuous process of the buffer layer and the gallium oxide film is more facilitated.
Drawings
Fig. 1 is a flow chart of the continuous process of the present invention for producing a gallium oxide thin film layer.
FIG. 2 is a schematic flow diagram of a prior art discontinuous process.
Fig. 3 is a schematic structural view of a gallium oxide thin film on a silicon substrate according to the invention.
FIG. 4 is a process flow diagram of a continuous process for preparing a hafnium oxide buffer layer and a gallium oxide thin film layer using atomic layer deposition according to the present invention.
FIGS. 5 (a), (b) and (c) are surface mirror images of gallium oxide thin films prepared on substrates of silicon (100), (110) and (111) without buffer layer prepared in comparative example 1, respectively.
FIGS. 6 (a), (b) and (c) are surface mirror images of gallium oxide films on silicon (100), (110) and (111) substrates, respectively, on which the hafnium oxide buffer layer prepared in example 1 acts.
Fig. 7 is an atomic force microscope photograph of the surface of a gallium oxide film on a silicon (100) substrate on which a hafnium oxide buffer layer is formed as in example 1.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings and examples, so that the implementation process of how the present invention can be applied to solve the technical problems and achieve the technical effects is fully understood and implemented.
The structure of the gallium oxide film prepared on the silicon substrate is shown in figure 3, and the gallium oxide film comprises the silicon substrate, the hafnium oxide buffer layer and the gallium oxide film layer from bottom to top. The silicon substrate comprises three crystal faces (100), (110) and (111), the thickness of the hafnium oxide buffer layer is 30nm to 70nm, and the thickness of the gallium oxide film layer is 50nm to 200nm.
The conventional process for preparing the gallium oxide film layer with the buffer layer is generally as shown in fig. 2, and the buffer layer and the gallium oxide film layer are respectively prepared by adopting discontinuous processes. The process has long manufacturing period, the buffer layer and the gallium oxide film are intermittent in the preparation process, and the interface state can be changed in the process of waiting for the gallium oxide film preparation after the buffer layer preparation is finished, so that the growth quality of the gallium oxide film and the application prospect of corresponding microelectronic devices are affected.
In order to solve the problems, as shown in fig. 1, the buffer layer and the gallium oxide film are prepared by adopting a continuous process, and after the atomic layer deposition system is provided with the corresponding flow program as shown in fig. 4, the buffer layer and the gallium oxide film can be prepared in sequence, so that the time is saved, the interface state is not changed, and the production quality of the gallium oxide film can be improved.
The specific continuous production process of the invention is as follows:
Step 1) cleaning a silicon substrate: firstly, removing a silicon dioxide layer on the silicon surface by using hydrofluoric acid, and then respectively ultrasonically cleaning for 10 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence.
Step 2) adopting a continuous process of an atomic layer deposition method to prepare a buffer layer and a gallium oxide film layer: comprises a hafnium oxide buffer layer with 300-700 cycle period and a gallium oxide film layer with 1000-4000 cycle period. The vacuum degree is less than 1Torr, the substrate temperature is 230-280 ℃, the carrier gas is argon, and the flow is 20sccm.
Wherein each cycle of the hafnium oxide buffer layer comprises four pulses: adopting a hafnium source pulse taking TEMAH as a source, wherein the pulse time is 0.15s; the time of the purging pulse under the action of argon is 5s; an oxygen source pulse with ozone as a source is adopted, and the pulse time is 5s; the time of the argon-operated purge pulse was 10s.
Wherein each cycle of the gallium oxide thin film layer comprises four pulses: gallium source pulse with TEG or TMG as source is adopted, and the pulse time is 0.1s or 0.015s; the time of the purging pulse under the action of argon is 5s; an oxygen source pulse with ozone as a source is adopted, and the pulse time is 5s; the time of the argon-operated purge pulse was 10s.
And 3) carrying out high-temperature annealing by adopting an annealing furnace: the annealing atmosphere is nitrogen, the temperature is 900 ℃, and the annealing time is 10min.
To better demonstrate the advantages of the continuous production process of the present invention, the following is verified by means of specific examples.
Example 1
Step 1), cleaning a silicon substrate, and placing the cleaned silicon substrate into an atomic layer deposition chamber;
Step 2), adjusting the vacuum degree in the atomic layer deposition chamber to be less than 1Torr, heating the silicon substrate to 250 ℃, and sequentially preparing a hafnium oxide buffer layer and a gallium oxide film layer by adopting a continuous process of an atomic layer deposition method; which comprises a 500 cycle period hafnium oxide buffer layer and a 2000 cycle period gallium oxide thin film layer.
Wherein each cycle of the hafnium oxide buffer layer comprises four pulses: adopting a hafnium source pulse taking TEMAH as a source, wherein the pulse time is 0.15s; the time of the purging pulse under the action of argon is 5s; an oxygen source pulse with ozone as a source is adopted, and the pulse time is 5s; the time of the argon-operated purge pulse was 10s.
Wherein each cycle of the gallium oxide thin film layer comprises four pulses: gallium source pulse with TEG as source is adopted, and the pulse time is 0.1s; the time of the purging pulse under the action of argon is 5s; an oxygen source pulse with ozone as a source is adopted, and the pulse time is 5s; the time of the argon-operated purge pulse was 10s.
And 3) carrying out high-temperature annealing to obtain the high-quality gallium oxide film on the silicon substrate.
Comparative example 1
Step 1), cleaning a silicon substrate, and placing the cleaned silicon substrate into an atomic layer deposition chamber;
Step 2) adjusting the vacuum degree in the atomic deposition chamber to be less than 1Torr, heating the silicon substrate to 250 ℃, and directly depositing a gallium oxide layer on the silicon substrate by adopting an atomic layer deposition method.
And 3) carrying out high-temperature annealing to obtain the gallium oxide film on the silicon substrate.
Fig. 5 and 6 are mirror images of the surface of a gallium oxide film on a silicon substrate without a buffer layer and under the action of the buffer layer using the process of the present invention, respectively. From the graph, the surface of the gallium oxide film directly grown without the buffer layer shows obvious flower-like defects, which are essentially surface cracks generated by stress induction. On the other hand, under the action of the hafnium oxide buffer layer, the gallium oxide thin films on the silicon substrate have flat surfaces and do not show flower-shaped crack defects.
Fig. 7 is an atomic force microscope image of the surface of a gallium oxide film on a silicon (100) substrate with a hafnium oxide buffer layer using the process of the present invention. The gallium oxide film can be seen to have a flat surface, and the surface roughness is as low as 3.27nm, which proves good growth quality.
The foregoing is merely specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any changes or substitutions (such as substitution of buffer layer structure, and change of growth method, selection of buffer layer material, etc.) that are easily conceivable by those skilled in the art within the scope of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A method for preparing a gallium oxide film on a silicon substrate, characterized by comprising the following steps:
step 1), cleaning a silicon substrate, and placing the cleaned silicon substrate into an atomic layer deposition chamber;
Step 2), adjusting the vacuum degree in the atomic layer deposition chamber to be less than 1Torr, heating the silicon substrate to 230-280 ℃, and sequentially preparing a hafnium oxide buffer layer and a gallium oxide film layer by adopting a continuous process of an atomic layer deposition method;
And 3) carrying out high-temperature annealing to obtain the high-quality gallium oxide film on the silicon substrate.
2. A method for producing a gallium oxide film on a silicon substrate according to claim 1, wherein: the thickness of the hafnium oxide buffer layer is 30nm to 70nm.
3. A method for producing a gallium oxide film on a silicon substrate according to claim 1 or 2, wherein: the thickness of the gallium oxide film layer is 50nm to 200nm.
4. A method for producing a gallium oxide film on a silicon substrate according to claim 3, wherein: the atomic layer deposition method continuous process in the step 2) comprises a hafnium oxide buffer layer with 300-700 cycle period and a gallium oxide film layer with 1000-4000 cycle period.
5. A method for producing a gallium oxide film on a silicon substrate according to claim 4, wherein: each cycle of the hafnium oxide buffer layer comprises four pulses, a hafnium source pulse using TEMAH as a source, an oxygen source pulse using ozone as a source, and a purge pulse using argon.
6. A method for producing a gallium oxide film on a silicon substrate according to claim 4, wherein: each period of the gallium oxide film layer comprises four pulses, a gallium source pulse with TEG or TMG as a source, an oxygen source pulse with ozone as a source and a purge pulse with argon.
7. A method for producing a gallium oxide film on a silicon substrate according to claim 1, wherein: the specific process of high-temperature annealing in the step (3) comprises the following steps: annealing is carried out by an annealing furnace, the annealing atmosphere is nitrogen, the temperature is 900 ℃, and the annealing time is 10min.
8. A method for producing a gallium oxide film on a silicon substrate according to claim 1, wherein: the specific steps of cleaning the silicon substrate in the step 1) are as follows: firstly, removing a silicon dioxide layer on the silicon surface by using hydrofluoric acid, and then respectively ultrasonically cleaning for 10 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence.
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