CN113659017B - Gallium arsenide wafer and preparation method thereof - Google Patents
Gallium arsenide wafer and preparation method thereof Download PDFInfo
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- CN113659017B CN113659017B CN202110885972.3A CN202110885972A CN113659017B CN 113659017 B CN113659017 B CN 113659017B CN 202110885972 A CN202110885972 A CN 202110885972A CN 113659017 B CN113659017 B CN 113659017B
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 53
- 238000002161 passivation Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 35
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 6
- 210000002381 plasma Anatomy 0.000 claims description 85
- 238000012545 processing Methods 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 6
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 108
- 239000000523 sample Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 201000003549 spinocerebellar ataxia type 20 Diseases 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000013383 initial experiment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 organic matters Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
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- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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- 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
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1856—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising nitride compounds, e.g. GaN
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/02—Structural details or components not essential to laser action
- H01S5/0206—Substrates, e.g. growth, shape, material, removal or bonding
- H01S5/0211—Substrates made of ternary or quaternary compounds
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- H01S5/00—Semiconductor lasers
- H01S5/02—Structural details or components not essential to laser action
- H01S5/028—Coatings ; Treatment of the laser facets, e.g. etching, passivation layers or reflecting layers
- H01S5/0281—Coatings made of semiconductor materials
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- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/02—Structural details or components not essential to laser action
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- H01S5/0282—Passivation layers or treatments
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- H01S2304/00—Special growth methods for semiconductor lasers
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Abstract
The present invention relates to a gallium arsenide wafer, one surface of the gallium arsenide wafer is provided with a gallium nitride passivation layer, the root mean square roughness of the gallium arsenide wafer surface on the side provided with the gallium nitride passivation layer is not higher than 0.22nm, the contact angle is not higher than 4 degrees, the root mean square roughness of the gallium arsenide wafer surface is measured by using an atomic force microscope, and the contact angle is measured by using a contact angle measuring instrument. The invention also relates to a preparation method of the gallium arsenide wafer, which comprises the following steps: and (3) treating the surface of the initial gallium arsenide wafer by nitrogen and hydrogen mixed plasma formed by the mixed gas of nitrogen and hydrogen under the action of a remote radio frequency source and forming a gallium nitride passivation layer. The gallium arsenide wafer has good controllability and stability, small surface roughness, fewer defects and super hydrophilicity, greatly improves the performance of the gallium arsenide wafer, and can provide a high-quality substrate for subsequent process application.
Description
Technical Field
The present invention relates to semiconductor wafers and methods for fabricating the same, and more particularly, to a gallium arsenide wafer with a gallium nitride passivation layer and a method for fabricating the same.
Background
Gallium arsenide (GaAs) is an important III-V semiconductor compound material, and is widely used in solar cells, semiconductor lasers, and the like because of its characteristics such as high electron mobility, high luminous efficiency, and the like. In the production of gallium arsenide wafers, various pollutants such as organic matters, dust and the like are often attached to the surface of gallium arsenide in the air, an oxide layer is easy to form on the surface, a thicker oxide layer can form higher surface state and interface state density, and the existence of the problems can change the performance of the gallium arsenide material so as to influence the application of the gallium arsenide material.
At present, in order to ensure the use stability of gallium arsenide materials, domestic and foreign expert scholars have studied a gallium arsenide surface modification method, mainly a passivation technology, more commonly a sulfur passivation technology, which generally utilizes a sulfur-containing chemical reagent to treat the gallium arsenide surface to generate a sulfur-containing passivation layer on the gallium arsenide surface, for example, "A comprison ofS-passivation of III-V (001) surface use (NH) 4 ) 2 S x and S 2 Cl 2 Gnoth, D.N. et al, applied Surface Science,1998, volumes 123-124, pages 120-125 "and" Surface passivation and morphology of GaAs (100) processed in HCl-isopropanol solution, alperovich, VL et al, applied Surface Science,2004, volume 235, pages 249-259). Sulfur passivation technology reduces oxidation of gallium arsenide surfaces in air, but reagents used in the fabrication process not only pollute the environment but also easily adhere to gallium arsenide surfaces to form contaminants, and these residual materials can affect the stability of semiconductor devices. In addition, the effect of sulfur passivation is unstable, and passivation failure can be caused under the aerobic atmosphere environment and the light irradiation condition. Another common technique is dry passivation, which is mainly to grow a layer of thin film silicon material on the pretreated gallium arsenide surface by sputtering. The method avoids the problems of stability and environmental pollution in wet passivation, but has larger surface defects introduced in the pretreatment process, and the formed silicon film is made of polycrystalline material, so that the control difficulty of process precision is large and the repeatability is poor. In addition, the patent application No. 201511023310.6 proposes a method for modifying the surface of gallium arsenide material by plasma passivation technology, which uses gas plasma to modify the surface of gallium arsenide material and form new passivation on the surface of gallium arsenide materialLayers, but the process steps of the method are complex, the gas types are many, the efficiency is low, and the gas contains CCl 2 F 2 And NH 3 And corrosive gases, which not only cause equipment damage and environmental pollution, but also cause the obtained gallium arsenide material to have larger surface defects and influence the performance and stability of the gallium arsenide material.
Disclosure of Invention
In view of the problems existing in the prior art, in one aspect, the present invention provides a gallium arsenide wafer, one surface of the gallium arsenide wafer has a gallium nitride passivation layer, and the root mean square roughness of the gallium arsenide wafer surface on the side with the gallium nitride passivation layer is not higher than 0.22nm, the contact angle is not higher than 4 °, the root mean square roughness of the gallium arsenide wafer surface is measured using an atomic force microscope, and the contact angle is measured using a contact angle measuring instrument.
In another aspect, the present invention provides a method for preparing the gallium arsenide wafer according to the present invention, comprising the steps of:
(1) Placing the initial gallium arsenide wafer in a processing chamber of plasma cleaning equipment, and vacuumizing;
(2) Introducing mixed gas of nitrogen and hydrogen into the plasma chamber, and forming nitrogen and hydrogen mixed plasma under the action of a remote radio frequency source;
(3) And (3) leading the nitrogen and hydrogen mixed plasma obtained in the step (2) to enter a processing chamber, processing the surface of the initial gallium arsenide wafer and forming a passivation layer of gallium nitride.
Unexpectedly, the gallium arsenide wafer with the gallium nitride passivation layer has good controllability and stability, small surface roughness, fewer defects and super hydrophilicity, greatly improves the performance of the gallium arsenide wafer, and can provide a high-quality substrate for subsequent process application. The method has less damage to the surface of the gallium arsenide wafer, can not pollute the surface of the gallium arsenide wafer, greatly simplifies the process steps, has high efficiency and repeatability, and is environment-friendly.
Drawings
Fig. 1 is an atomic force photograph of a gallium arsenide wafer surface processed using one embodiment of the present invention.
Fig. 2 is a graph of contact angle of gallium arsenide wafer surfaces before and after processing using an embodiment of the present invention: (a) prior to treatment; (b) after treatment.
Fig. 3 is an X-ray photoelectron spectrum of a gallium nitride passivation layer formed on the surface of a gallium arsenide wafer processed using one embodiment of the invention.
FIG. 4 is a steady state fluorescence spectrum of a gallium arsenide wafer before and after processing using an embodiment of the invention: (a) prior to treatment; (b) after treatment.
Detailed Description
In a first aspect, the present invention provides a gallium arsenide wafer having a gallium nitride passivation layer on one surface thereof, and the gallium arsenide wafer surface on the side having the gallium nitride passivation layer has a root mean square roughness of not more than 0.22nm, preferably not more than 0.19nm, a contact angle of not more than 4 °, preferably not more than 3 °, the root mean square roughness of the gallium arsenide wafer surface being determined using an atomic force microscope, and the contact angle being determined using a contact angle measuring instrument.
In the invention, the root mean square roughness of the gallium arsenide wafer surface can be measured by a C3000 atomic force microscope of Nanosurf company, switzerland, the type of the probe used is Tap190Al-G, the scanning range is 5 μm×5 μm, and the scanning speed is 0.78s/line. The result obtained by the detection of the instrument is root mean square roughness, and the unit is nm.
In the invention, the contact angle of the gallium arsenide wafer surface can be measured by an OCA20 contact angle measuring instrument of DataPhysics company in Germany, the static contact angle of deionized water is measured, the volume of water drop is about 3 mu L, the measuring precision is + -0.1 DEG, and analysis and calculation are carried out by using SCA20 contact angle measuring software.
In the present invention, the gallium nitride passivation layer can be measured by PHI5000Versaprobe X-ray photoelectron spectroscopy of Ulvac-Phi company of Japan, and the vacuum degree is higher than 3×10 -6 Pa, alK alpha rays, power 25W, narrow scanning pass energy 23.5eV.
In a preferred embodiment, the gallium arsenide wafer surface has a root mean square roughness of 0.18-0.19nm.
In a preferred embodiment, the contact angle of the gallium arsenide wafer surface is 1.8 ° to 2.8 °.
The surface of the gallium arsenide wafer is easily oxidized in the air, so that the high surface state density is caused, and the photoelectric performance and stability of the gallium arsenide wafer are affected. The gallium arsenide wafer surface of the invention has gallium nitride passivation layer, which not only effectively prevents gallium arsenide from oxidation and reduces gallium arsenide surface state density, improves gallium arsenide wafer performance, but also has good stability in air environment for a long time.
In a second aspect, the present invention provides a method for preparing the gallium arsenide wafer, comprising the steps of:
(1) Placing the initial gallium arsenide wafer in a processing chamber of plasma cleaning equipment, and vacuumizing;
(2) Introducing mixed gas of nitrogen and hydrogen into the plasma chamber, and forming nitrogen and hydrogen mixed plasma under the action of a remote radio frequency source;
(3) And (3) leading the nitrogen and hydrogen mixed plasma obtained in the step (2) to enter a processing chamber, processing the surface of the initial gallium arsenide wafer and forming a passivation layer of gallium nitride.
The mixed gas of nitrogen and hydrogen forms stable nitrogen and hydrogen mixed plasma under the action of a radio frequency source, on one hand, the mixed plasma accelerates to bombard the surface of the gallium arsenide wafer, and macromolecular pollutants on the surface of the mixed plasma are ionized into small molecules to be vaporized and pumped by a vacuum system, so that the effect of physically cleaning the gallium arsenide wafer is achieved; on the other hand, the hydrogen plasma and the gallium arsenide wafer surface have chemical action, so that the oxide on the gallium arsenide wafer surface can be effectively removed, and more advantageously, the nitrogen plasma and the gallium arsenide wafer surface react to form a gallium nitride passivation layer with good stability, namely, the effect of chemically cleaning the gallium arsenide wafer is achieved. Therefore, through the physicochemical effect of nitrogen and hydrogen mixed plasmas on the gallium arsenide wafer, not only can the pollutants on the surface of the gallium arsenide wafer be effectively removed, but also a stable gallium arsenide passivation layer is formed on the surface of the gallium arsenide wafer, and meanwhile, the processed gallium arsenide wafer has super-hydrophilicity, so that the surface state density of the gallium arsenide wafer is effectively reduced, and the performance of the gallium arsenide wafer is greatly improved. In addition, the gallium arsenide wafer is processed after the plasma is formed in advance, so that the damage (surface defect) caused by the bombardment of the plasma on the surface of the wafer can be reduced as much as possible while the wafer is thoroughly cleaned, the surface roughness of the processed wafer is small, and the finally obtained gallium arsenide wafer with the gallium nitride passivation layer has good controllability and stability.
In the method of the invention, the temperature is room temperature and the pressure is atmospheric pressure during operation.
In step (1) of the method of the invention, the surface of the gallium arsenide wafer to be subjected to surface treatment as an initial wafer is the wafer surface after being subjected to rough polishing, finish polishing, cleaning (for example, cleaning by using a known ammonia, hydrogen peroxide and water (SC-1) system) and drying treatment by using a known method.
The plasma cleaning apparatus used was equipped with a remote plasma source, such as tergo-plus plasma cleaner manufactured by us PIE SCIENTIFIC LLC.
In step (2) of the method of the present invention, the flow rate of the mixed gas of nitrogen and hydrogen gas is 5-50sccm (i.e., standard cm) 3 Per minute), preferably 7-30sccm, more preferably 8.5-15sccm.
In the mixed gas of the nitrogen and the hydrogen, the volume ratio of the nitrogen to the hydrogen is 85:15-98:2, preferably 88:12-97:3, and more preferably 89:11-93:7.
The remote RF source is used at a power of 50-150W, preferably 60-120W, more preferably 75-110W per liter of plasma chamber.
In step (3) of the method, the treatment time of the nitrogen and hydrogen mixed plasma on the surface of the initial gallium arsenide wafer is 2-20min, preferably 5-15min, and more preferably 8-12min.
In step (3) of the method of the present invention, the preferred nitrogen and hydrogen mixed plasma is obtained using the following conditions: flow of a mixture of nitrogen and hydrogenIn an amount of 5-50sccm (i.e. standard cm) per liter of plasma chamber 3 Per minute), preferably 7-30sccm, more preferably 8.5-15sccm; in the mixed gas of the nitrogen and the hydrogen, the volume ratio of the nitrogen to the hydrogen is 85:15-98:2, preferably 88:12-97:3, and more preferably 89:11-93:7; the remote RF source is used at a power of 50-150W, preferably 60-120W, more preferably 75-110W per liter of plasma chamber.
The volume ratio of the plasma chamber to the processing chamber is 1.5:1-1:1.5; preferably 1.2:1 to 1:1.2, most preferably 1.05:1 to 1:1.05.
Further preferably, per cm relative to a single side 2 The flow rate of the mixed gas of nitrogen and hydrogen used for the initial wafer surface of the area is 0.114-1.136sccm, preferably 0.159-0.682sccm, more preferably 0.193-0.341sccm, per liter of plasma chamber; the power of the remote RF source used is 1.2-3.4W, preferably 1.4-2.7W, more preferably 1.7-2.5W per liter of plasma chamber.
For example, for a 75mm diameter wafer, the plasma can be obtained using the following conditions: the flow rate of the mixed gas of the nitrogen and the hydrogen is 5-50sccm, preferably 7-30sccm, more preferably 8.5-15sccm, per liter of the plasma chamber; in the mixed gas of the nitrogen and the hydrogen, the volume ratio of the nitrogen to the hydrogen is 85:15-98:2, preferably 88:12-97:3, and more preferably 89:11-93:7; the remote RF source is used at a power of 50-150W, preferably 60-120W, more preferably 75-110W per liter of plasma chamber. In the processing chamber, for example, 1-3 wafers may be processed simultaneously.
In the method of the invention, no further treatment steps are interposed between steps (1) to (3).
In the method of the present invention, the process chamber and the ion chamber are each chambers having independent spatial structures.
In the present invention, the definition in the broadest scope and each preferred definition can be combined with each other to form a new technical solution, and are also regarded as being disclosed in the present specification.
The present invention is illustrated below by way of examples, which should not be construed as limiting the scope of the invention.
Examples
I. Instrument for measuring and controlling the intensity of light
A plasma cleaning apparatus (tergo-plus plasma cleaner manufactured by us PIE SCIENTIFIC LLC) equipped with a remote plasma source.
A plasma cleaning device (Diener plasma cleaning machine, germany) equipped with a direct radio frequency plasma source.
II. Initial experiment wafer
As no other explanation, a gallium arsenide wafer having a diameter of 75mm and a thickness of 300 μm was used as the starting wafer, and the surface to be surface-treated was rough polished, finish polished, subjected to an ammonia, hydrogen peroxide and water (SC-1) system (5%, 7% and 88% by weight, respectively), and dried.
III, detecting a gallium arsenide wafer:
gallium nitride passivation layer on wafer surface: PHI5000Versaprobe X-ray photoelectron spectroscopy (Ulvac-Phi Co., japan) was used, and the vacuum degree was higher than 3×10 -6 Pa, alK alpha rays (1486.6 eV), power 25W, narrow scan pass energy 23.5eV.
Root mean square roughness of wafer surface: a C3000 atomic force microscope from Nanosurf, switzerland was used, the probe type used was Tap190Al-G, the scanning range was 5. Mu.m.times.5. Mu.m, and the scanning speed was 0.78s/line.
Contact angle of wafer surface: the static contact angle of deionized water was measured using an OCA20 contact angle measuring instrument from Dataphysics, germany, the volume of the water drop was about 3 μl, the measurement accuracy was ±0.1°, and analysis calculation was performed using SCA20 contact angle measuring software.
Steady state fluorescence spectrum (PL) performance of wafer: an RPM2000 fluorescence spectrometer from Bio2 Rad, U.S.A., was used, the laser wavelength was 532.0nm, the laser power was 4.87mW, the slit width was 0.1mm, and the spectral scan resolution was 1.02nm.
Comparative example 1
A german Diener plasma cleaning machine was used, which was equipped with a direct rf plasma source. Placing single initial gallium arsenide wafer on sample stage of vacuum chamber, vacuumizing, introducing N into the chamber 2 And H 2 The flow rate of the mixed gas is 10sccm, wherein the content of hydrogen in the mixed gas is 10 percent, the radio frequency power is applied to 100W, the surface of the gallium arsenide wafer is treated for 10 minutes, the gas is stopped being introduced, the vacuumizing is stopped, and the gas is exhausted, so that the surface modification of the gallium arsenide wafer is completed.
Comparative example 2
A german Diener plasma cleaning machine was used, which was equipped with a direct rf plasma source. Placing single initial gallium arsenide wafer on sample stage of vacuum chamber, vacuumizing, introducing N into the chamber 2 And applying radio frequency power of 100W to treat the surface of the gallium arsenide wafer for 10min, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Comparative example 3
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 The gas flow is 10sccm, and the radio frequency power is applied to 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen plasma for 10min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 1
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 And H 2 Wherein the gas flow is 10sccm, the hydrogen content in the mixed gas is 10%, and the radio frequency power is applied to the mixed gas at 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 10min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 2
Using tergo-plus plasma cleaner manufactured by us PIE SCIENTIFIC LLC,the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 And H 2 The gas flow is 15sccm, wherein the content of hydrogen in the mixed gas is 10 percent, and the radio frequency power is applied to the mixed gas by 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 10min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 3
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 And H 2 The gas flow is 50sccm, wherein the content of hydrogen in the mixed gas is 10 percent, and the radio frequency power is applied to the mixed gas by 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 10min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 4
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 And H 2 Wherein the gas flow is 10sccm, the hydrogen content in the mixed gas is 10%, and the radio frequency power is applied to the mixed gas at 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 5min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 5
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; to remote plasma chamberN is introduced into the chamber 2 And H 2 Wherein the gas flow is 10sccm, the hydrogen content in the mixed gas is 10%, and the radio frequency power is applied to the mixed gas at 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 15min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Example 6
Using tergo-plus plasma cleaner, manufactured by us PIE SCIENTIFIC LLC, the apparatus is equipped with a remote plasma source. Placing a single initial gallium arsenide wafer on a sample stage of a processing chamber, and vacuumizing; introducing N into a remote plasma chamber 2 And H 2 The gas flow is 10sccm, wherein the content of hydrogen in the mixed gas is 7%, and the radio frequency power is applied to the mixed gas by 100W; and (3) treating the surface of the gallium arsenide wafer by using nitrogen and hydrogen mixed plasmas for 5min to form a passivation layer of gallium nitride, stopping introducing gas, stopping vacuumizing and exhausting to finish the modification of the surface of the gallium arsenide wafer.
Gallium arsenide wafers were inspected using the method described in section III and the results are summarized in table 1.
TABLE 1
As can be seen from Table 1, the gallium arsenide wafer processed by the method of the invention has small surface roughness, fewer defects and super hydrophilicity, and the PL performance of the processed gallium arsenide wafer is greatly improved, which can provide a good substrate for the subsequent process application.
Fig. 1 is an atomic force photograph of a gallium arsenide wafer surface with a gallium nitride passivation layer treated by the method of example 1, and the root mean square roughness of the wafer surface is 0.1888nm after software analysis, which indicates that the treatment by the method of the invention does not cause great damage to the gallium arsenide wafer surface and does not generate structural defects. Fig. 2 is a photograph of the contact angle of an untreated gallium arsenide wafer and a gallium arsenide wafer surface having a gallium nitride passivation layer treated by the method of example 1, and it is apparent from the figure that the contact angle is reduced from 63.9 ° to 2.6 °, which illustrates the transition from hydrophobic to super-hydrophilic of the gallium arsenide wafer surface after the treatment by the method of the present invention. Fig. 3 is an X-ray photoelectron spectrum of the surface of the gallium arsenide wafer processed by the method of example 1, and the result shows that the gallium nitride passivation layer is formed on the surface of the gallium arsenide wafer processed by the method of the invention, namely, the Ga-N peak appears at the 397.9eV position, and the stable gallium nitride passivation layer can play a better role in protecting the gallium arsenide surface, reduce the surface state density of the gallium arsenide wafer, thereby improving the PL performance of the gallium arsenide wafer. Fig. 4 is a comparison of PL spectra of an untreated gallium arsenide wafer and a gallium arsenide wafer having a gallium nitride passivation layer treated using the method of example 1, showing an increase in PL intensity of 468.2% for gallium arsenide wafers treated using the method of the present invention.
Although the present invention has been described with reference to particular embodiments, those skilled in the art will recognize that changes and modifications may be made to the embodiments without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (11)
1. A method of fabricating a gallium arsenide wafer, comprising the steps of:
(1) Placing the initial gallium arsenide wafer in a processing chamber of plasma cleaning equipment, and vacuumizing;
(2) Introducing mixed gas of nitrogen and hydrogen into the plasma chamber, and forming nitrogen and hydrogen mixed plasma under the action of a remote radio frequency source;
(3) The nitrogen and hydrogen mixed plasmas obtained in the step (2) enter a processing chamber to process the surface of the initial gallium arsenide wafer and form a passivation layer of gallium nitride,
wherein the flow rate of the mixed gas of the nitrogen and the hydrogen which is introduced in the step (2) is 5-50sccm per liter of the plasma chamber,
in the mixed gas of the nitrogen and the hydrogen, the volume ratio of the nitrogen to the hydrogen is 89:11-93:7, the power of the remote radio frequency source in the step (2) is 75-110W per liter of plasma chamber,
the treatment time of the nitrogen and hydrogen mixed plasmas on the surface of the initial gallium arsenide wafer in the step (3) is 5-15min,
the gallium arsenide wafer is obtained: the gallium arsenide wafer has a gallium nitride passivation layer on one surface, and the gallium arsenide wafer surface on the side with the gallium nitride passivation layer has a root mean square roughness of not higher than 0.19nm, a contact angle of not higher than 3.1 °, the root mean square roughness of the gallium arsenide wafer surface is measured using an atomic force microscope, and the contact angle is measured using a contact angle measuring instrument.
2. The method of claim 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen introduced in the step (2) is 7-30sccm per liter of the plasma chamber.
3. The method of claim 1, wherein the flow rate of the mixed gas of nitrogen and hydrogen introduced in the step (2) is 8.5-15sccm per liter of the plasma chamber.
4. A method according to any one of claims 1 to 3, characterized in that per cm relative to a single side 2 The flow rate of the mixed gas of nitrogen and hydrogen used for the initial wafer surface of the area is 0.114-1.136sccm per liter of plasma chamber.
5. The method according to claim 4, wherein the ratio of the number of the electrodes to the number of the electrodes is one 2 The flow rate of the mixed gas of nitrogen and hydrogen used for the initial wafer surface of the area is 0.159-0.682sccm per liter of plasma chamber.
6. The method according to claim 4, wherein the ratio of the number of the electrodes to the number of the electrodes is one 2 The flow rate of the mixed gas of nitrogen and hydrogen used for the initial wafer surface of the area is 0.193-0.341sccm per liter of plasma chamber.
7. A method according to any one of claims 1 to 3, characterized in that the volume ratio of the plasma chamber to the process chamber is 1.5:1-1:1.5.
8. The method of claim 7, wherein a volume ratio of the plasma chamber to the processing chamber is 1.2:1 to 1:1.2.
9. The method of claim 7, wherein a volume ratio of the plasma chamber to the processing chamber is 1.05:1 to 1:1.05.
10. Gallium arsenide wafer obtained according to the method of any of claims 1 to 9, characterized in that one surface of the gallium arsenide wafer has a gallium nitride passivation layer and the root mean square roughness of the gallium arsenide wafer surface on the side with gallium nitride passivation layer is not higher than 0.19nm, the contact angle is not higher than 3.1 °, the root mean square roughness of the gallium arsenide wafer surface is determined using an atomic force microscope and the contact angle is determined using a contact angle meter.
11. Gallium arsenide wafer according to claim 10, characterized in that the contact angle of the gallium arsenide wafer surface on the side with the gallium nitride passivation layer is not more than 3 °.
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| US5336361A (en) * | 1990-03-23 | 1994-08-09 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing an MIS-type semiconductor device |
| CN105513948A (en) * | 2015-12-30 | 2016-04-20 | 西安立芯光电科技有限公司 | Novel method for modifying GaAs material surface |
| JP2020177970A (en) * | 2019-04-16 | 2020-10-29 | 住友電気工業株式会社 | Gallium arsenide substrate, epitaxial substrate, manufacturing method of gallium arsenide substrate, and manufacturing method of epitaxial substrate |
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| US5336361A (en) * | 1990-03-23 | 1994-08-09 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing an MIS-type semiconductor device |
| CN105513948A (en) * | 2015-12-30 | 2016-04-20 | 西安立芯光电科技有限公司 | Novel method for modifying GaAs material surface |
| JP2020177970A (en) * | 2019-04-16 | 2020-10-29 | 住友電気工業株式会社 | Gallium arsenide substrate, epitaxial substrate, manufacturing method of gallium arsenide substrate, and manufacturing method of epitaxial substrate |
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