CN1241019A - Process for using sulfur to passivate surface of semiconductor made of group IIIA-VA compounds - Google Patents
Process for using sulfur to passivate surface of semiconductor made of group IIIA-VA compounds Download PDFInfo
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- CN1241019A CN1241019A CN 98115739 CN98115739A CN1241019A CN 1241019 A CN1241019 A CN 1241019A CN 98115739 CN98115739 CN 98115739 CN 98115739 A CN98115739 A CN 98115739A CN 1241019 A CN1241019 A CN 1241019A
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Abstract
A process for using sulfur to passivate the surface of semiconductor made of the compounds of group IIIA-VA features that the surface of semiconductor is dipped in 0.03-3.3M aqueous solution of thioamide at ordinary temp-100 deg.C for 0.5-120min. Said passivating liquid has high stability and adaptability. The sulfide passivated layer is uniform and stable. Its advantages are simple equipment, low cost and easy operation.
Description
The present invention relates to III
A-V
ACompound semiconductor surface treatment and process for fabrication of semiconductor device technical field.
III
A-V
ACompound semiconductor surface sulfur passivation is one of technology of device manufacturing, purpose is in order to eliminate oxide on surface, lower the blemish density of states, raising is as the surface quality of device substrate material and the performance and the stability of device, therefore the quality of passivation layer quality directly influences the epitaxial layer quality and even the device quality of device.III
A-V
AThe surperficial sulfur passivation of compound semiconductor carries out in inorganic sulfide solution usually.The sulfide passivation layer that adopts this method to form is not obvious, and easily by oxygen attack in the air, thereby cause passivation layer to lose efficacy.U.S.'s " Applied Physics communication " magazine (Appl.Phys.Lett., 64 (25), 1994,3425) was once reported a kind of with sulfur dichloride (S
2Cl
2) the surperficial method of passivation GaAs (GaAs), can effectively eliminate oxide on surface, form the sulfide passivation layer.But the sulfur dichloride that this method is used very easily absorbs water when being exposed in the air and decomposes, and hydrogen chloride that is decomposed to form (HCl) and hydrogen sulfide (H
2S) gas is poisonous, easily causes environmental pollution, so passivating solution needs matching while using, can not put for a long time, causes operational inconvenience; Sulfur dichloride is a severe corrosive reagent in addition, and the passivating process reaction speed is too fast, is difficult to control, causes semiconductor surface damage and destruction easily.U.S.'s " vacuum science technical journal " (J.Vac.Sci.Technol.B, 11 (2), 1993,195) has reported the method for ammonia microwave plasma passivation GaAs.This method offsets except that the arsenic oxide effect of gallium arsenide surface better, but not obvious to the elimination of surperficial gallium oxide, so passivation effect is undesirable.U.S.'s " applicating physical magazine " (J.Appl.Phys., 78 (4), 1995,2764) has reported a kind of method of electrochemistry anodic passivity gallium arsenide surface.This method can form the sulfide of very thick gallium and arsenic and the passivation layer that mixes of oxide on the surface, but because anodic current density is difficult to control the surface damage that also is corroded easily.
The objective of the invention is to propose a kind ofly can effectively eliminate III
A-V
AThe compound semiconductor oxide on surface also forms the passivating method of surface of stability sulfide passivation layer, to overcome the above-mentioned shortcoming of prior art.
This III
A-V
ACompound semiconductor surface sulfur passivation method is characterized in that it is in 0.03 to the 3.3M thioamides aqueous solution, in room temperature to 100 ℃ temperature range that semiconductor surface is immersed concentration, according to the variable concentrations and the temperature of passivating solution, places respectively 0.5 to 120 minute.
Described III
A-V
ACompound semiconductor is meant by III
AFamily's element comprises Al, Ga, In, with V
AFamily's element comprises P, As, Sb, and the binary of composition or multi-element compounds semiconductor comprise GaAs, GaSb, InP, InGaP, InAlAs, GaAlAsP.
Described thioamides is to consist of R-CSNH
2, water-soluble organic compound, wherein R represents hydrogen or hydrocarbyl group.
The aqueous solution of described thioamides can be acid, alkalescence or neutral.Because of the time that passivation under the neutrallty condition needs longer, generally select acidity or alkalescence for use.During passivation, the acidity of solution can select for use various acid reagents to regulate, and generally transfers to the pH value and is not less than 3 under acid condition; During passivation, the alkalescence of solution can select for use various alkaline reagents to regulate, and generally transfers to the pH value and is not more than 12 under alkali condition.In the mentioned reagent, be good with water-soluble organic acid and ammoniacal liquor, because they are acid, the alkali conditioning agent of comparison " gentleness ", not only regulating effect is good, and can avoid introducing foreign ion.
The dominant mechanism of the inventive method is as follows:
Because thioamides is strong polarity organic sulfur compound molecule, and is soluble in water, in the aqueous solution following hydrolysis can take place:
(1) in acid solution,
(2) in alkaline solution,
(3) in ammonia spirit,
No matter in acid, alkalescence or ammonia spirit, thioamides all can hydrolysis generate the sulphion (S with reactivity
2-) and sulphur hydrogen radical ion (HS
-), and self forms stable organic amide (R-CONH
2) and organic acid ammonium salt (R-COONH
4).Therefore its aqueous solution is more stable.HS
-And S
2-Ion again with III
A-V
AThe reaction of compound semiconductor generation surface/interface impels oxide on surface to decompose, and forms the sulfide passivation layer simultaneously.Because R-CSNH
2Hydrolysis is a process more slowly, and above-mentioned passivating process also slowly carries out, and this helps forming stabilized uniform sulfide passivation layer.
The inventive method has the following advantages:
(1) passivating solution that is adopted is more stable, places to undergo no deterioration in 2 to 3 weeks in air, and is easy to use;
(2) has extensive applicability, equal effective passivation III under acidity or alkali condition
A-V
AThe compound semiconductor surface forms stabilized uniform sulfide passivation layer.
(3) compare with other sulfur passivation method, significantly reduced toxic gas (as H
2S) effusion has reduced air pollution degree;
(4) equipment is simple, and cost is low;
(5) easy to operate, be easy to promote.
Below be embodiments of the invention.
Embodiment one: the passivation under acid condition
With The addition of C H
3CH
2CSNH
2Soluble in water, be mixed with the solution that concentration is 0.03M, add hydrochloric acid conditioning solution and become acid to pH ≈ 5.5.Indium antimonide (InSb), the InGaP (In of passivation will be desired
0.5Ga
0.5P) or phosphorus aluminum gallium arsenide (Ga
0.5Al
0.5As
0.9P
0.1) sample surfaces is dipped in the above-mentioned passivating solution, kept 30 minutes in room temperature (about 25 ℃).After taking out, the sample that passivation is good puts into acetone protection, to avoid introducing carbon and oxygen contamination.
Adopt Auger electron spectroscopy to detect to above-mentioned sample, have very strong oxygen characteristic signal before the passivation, through after the Passivation Treatment, the oxygen characteristic signal disappears, has occurred very strong sulphur characteristic signal simultaneously.Illustrate that above-mentioned processing eliminated the natural oxidizing layer of semiconductor surface effectively, and formed the sulfide passivation layer on the surface.
Embodiment two: the passivation under acid condition
With The addition of C H
3CSNH
2Soluble in water, be mixed with the solution that concentration is 3.3M, add the formic acid regulator solution to pH ≈ 3.GaAs (GaAs), the InGaP (In of passivation will be desired
0.5Ga
0.5P) or phosphorus aluminum gallium arsenide (Ga
0.5Al
0.5As
0.9P
0.1) sample is dipped in the above-mentioned passivating solution, takes out after 0.5 minute 100 ℃ of passivation, puts into acetone protection.
Embodiment three: the passivation under acid condition
With an amount of HCSNH
2Soluble in water, be mixed with the solution that concentration is 1.5M, add the acetate regulator solution to pH ≈ 6.2.Gallium antimonide (GaSb) or gallium phosphide (GaP) sample of desiring passivation are dipped in the above-mentioned passivating solution, take out after 20 minutes, put into acetone protection 60 ℃ of passivation.
Embodiment four: passivation under alkali condition
With The addition of C H
3CH
2CSNH
2Water-soluble, be mixed with the aqueous solution that concentration is 0.03M, with sodium hydrate regulator solution pH ≈ 12.0.The gallium antimonide (GaSb) of placement desire passivation or gallium phosphide (GaP) sample take out after 20 minutes in room temperature (25 ℃) passivation in above-mentioned passivating solution, put into acetone protection.
Embodiment five: passivation under alkali condition
With The addition of C H
3CSNH
2Be dissolved in the suitable quantity of water, be mixed with the solution that concentration is 1.65M, add ammoniacal liquor regulator solution pH ≈ 9.2.GaAs (GaAs), the InGaP (In of passivation will be desired
0.5Ga
0.5P) or phosphorus aluminum gallium arsenide (Ga
0.5Al
0.5As
0.9P
0.1) sample is positioned in this passivating solution, takes out after 20 minutes 90 ℃ of passivation, puts into acetone protection.
Embodiment six: passivation under alkali condition
With an amount of HCSNH
2Be dissolved in the suitable quantity of water, be mixed with the solution that concentration is 3.3M, add ammoniacal liquor regulator solution pH ≈ 8.5.Indium phosphide (InP), the aluminum gallium arsenide (Ga of passivation will be desired
0.5Al
0.5As) or aluminum phosphate indium (In
0.5Al
0.5P) sample is positioned in this passivating solution, takes out after 40 minutes 50 ℃ of passivation, puts into acetone protection.
Embodiment seven:
With The addition of C H
3CSNH
2Be dissolved in the suitable quantity of water, be mixed with the solution that concentration is 3.3M, add acetate regulator solution pH ≈ 7.GaAs (GaAs), the InGaP (In of passivation will be desired
0.5Ga
0.5P) or phosphorus aluminum gallium arsenide (Ga
0.5Al
0.5As
0.9P
0.1) sample is positioned in this passivating solution, takes out after 120 minutes 80 ℃ of passivation, puts into acetone protection.
Adopting Auger electron spectroscopy to detect to other samples in the foregoing description shows, through Passivation Treatment, can eliminate III effectively
A-V
ACompound semiconductor surface natural oxide, and formed stabilized uniform sulfide passivation layer on the surface, avoided the contamination of carbon and oxygen, obtained can be used for the backing material of device production and extension.
Claims (3)
1, a kind of III
A-V
ACompound semiconductor surface sulfur passivation method is characterized in that it is in 0.03 to 3.3M the thioamides aqueous solution that semiconductor surface is immersed concentration, in room temperature to 100 ℃ temperature range, places 0.5 to 120 minute; Described III
A-V
ACompound semiconductor is meant by III
AFamily's element and V
ABinary or multi-element compounds semiconductor that family's element is formed; Described thioamides is to consist of R-CSNH
2, water-soluble organic compound, wherein R represents hydrogen or hydrocarbyl group.
2, III according to claim 1
A-V
ACompound semiconductor surface sulfur passivation method is characterized in that the aqueous solution of described thioamides selects for use water-soluble organic acid to regulate, and makes the pH value be not less than 3.
3, III according to claim 1
A-V
ACompound semiconductor surface sulfur passivation method is characterized in that the aqueous solution of described thioamides selects for use ammoniacal liquor to regulate, and makes the pH value be not more than 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98115739 CN1099701C (en) | 1998-07-01 | 1998-07-01 | Process for using sulfur to passivate surface of semiconductor made of group IIIA-VA compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98115739 CN1099701C (en) | 1998-07-01 | 1998-07-01 | Process for using sulfur to passivate surface of semiconductor made of group IIIA-VA compounds |
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| Publication Number | Publication Date |
|---|---|
| CN1241019A true CN1241019A (en) | 2000-01-12 |
| CN1099701C CN1099701C (en) | 2003-01-22 |
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ID=5224710
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98115739 Expired - Fee Related CN1099701C (en) | 1998-07-01 | 1998-07-01 | Process for using sulfur to passivate surface of semiconductor made of group IIIA-VA compounds |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102339775A (en) * | 2011-09-23 | 2012-02-01 | 复旦大学 | Method for washing and purifying autologous oxide on surface of GaAs (gallium arsenide) and depositing Al2O3 medium |
| CN103578957A (en) * | 2013-11-01 | 2014-02-12 | 清华大学 | Substrate surface passivating method and semiconductor structure forming method |
| CN105070655A (en) * | 2015-07-15 | 2015-11-18 | 中国电子科技集团公司第四十六研究所 | Method for passivating gallium antimonide wafer |
| CN106784149A (en) * | 2016-12-28 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | A kind of passivating method of III V II-VI group solar cell |
-
1998
- 1998-07-01 CN CN 98115739 patent/CN1099701C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102339775A (en) * | 2011-09-23 | 2012-02-01 | 复旦大学 | Method for washing and purifying autologous oxide on surface of GaAs (gallium arsenide) and depositing Al2O3 medium |
| CN103578957A (en) * | 2013-11-01 | 2014-02-12 | 清华大学 | Substrate surface passivating method and semiconductor structure forming method |
| CN105070655A (en) * | 2015-07-15 | 2015-11-18 | 中国电子科技集团公司第四十六研究所 | Method for passivating gallium antimonide wafer |
| CN106784149A (en) * | 2016-12-28 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | A kind of passivating method of III V II-VI group solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1099701C (en) | 2003-01-22 |
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