CN102632055A - Method for cleaning sapphire substrate - Google Patents
Method for cleaning sapphire substrate Download PDFInfo
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- CN102632055A CN102632055A CN2012101019843A CN201210101984A CN102632055A CN 102632055 A CN102632055 A CN 102632055A CN 2012101019843 A CN2012101019843 A CN 2012101019843A CN 201210101984 A CN201210101984 A CN 201210101984A CN 102632055 A CN102632055 A CN 102632055A
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- sapphire substrate
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- cleaning
- substrate
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Abstract
The invention relates to a method for cleaning a sapphire substrate. The surface of a sapphire epitaxial substrate has a larger quality difference of the substrate surface and has a difference in defects of an oxidation layer and a subsurface after being cleaned by organic impurities and inorganic metal impurities due to chemical-mechanical polishing (CMP). The sapphire substrate is generally classified according to the cleaning conditions of the substrate surface. And when an imaging (PSS (Poly(sodium-p-styrenesulfonate))) substrate is prepared or heteroepitaxy is directly carried out, the product uniformity is different so that the final yield of the product is decreased. The method provided by the invention is characterized in that the sapphire substrate is cleaned with the organic impurities and the inorganic metal impurities and then is cleaned with hydrogen-nitrogen plasmas. After the cleaning method provided by the invention is carried out, the surface of the sapphire substrate has no oxidation impurities, defection layers and no subsurface defection layers. The surface quality of the substrate is good in consistency. The cleaning method provided by the invention has high yield of the PSS substrate or high crystallization quality of a GaN layer subjected to the heteroepitaxy.
Description
Technical field
The present invention relates to the processing technique field of crystalline material, especially a kind of cleaning method of Sapphire Substrate.
Background technology
Sapphire crystal (Al
2O
3) lattice constant mismatch rate between the epitaxial deposition film of C face and III-V and II-VI family is less, meets resistant to elevated temperatures requirement in the GaN brilliant processing procedure of heap of stone simultaneously, makes that sapphire single-crystal is indigo plant, the most frequently used backing material of white light LEDs luminescent material GaN of super brightness.For improving GaN crystalloid amount of heap of stone, can Sapphire Substrate be carried out graphically (PSS) processing, and crudy and employed Sapphire Substrate (substrate) the surface clean quality of the crystal mass of GaN crystalline substance of heap of stone and PSS are closely related.
At present, the organic impurities that general matting all adopts organic solvent to clean the Sapphire Substrate surface pollutes, and cooperates oxidant to clean the inorganic impurity and the metallic particles of Sapphire Substrate with inorganic acid, alkali again.Substrate surface organic impurities and inorganic metal impurity through the method is cleaned are less; But the oxide layer of substrate surface and sub-surface damage layer can't be removed; And the existence of the oxide layer of substrate surface and sub-surface damage layer will cause PSS technology and GaN brilliant technology instability of heap of stone, and yield is relatively poor.
Summary of the invention
The technical problem that the present invention will solve is: propose a kind of fairly perfect method for cleaning sapphire substrate, realize the perfection of Sapphire Substrate is cleaned.Sapphire Substrate surface non-oxidation layer, no surface damage and sub-surface damage layer through this method is cleaned all are improved the yield of PSS and the quality of GaN hetero-epitaxy.
The technical scheme that the present invention adopted is: a kind of cleaning method of Sapphire Substrate, this cleaning method are divided into the organic impurities pollution of removing substrate surface, oxide layer and the sub-surface damage layer of removing the pollution of substrate surface inorganic metal impurity and removing substrate surface.
For the organic impurities of removing substrate surface pollutes, adopt in the pure organic solvent of electronics and cleaned Sapphire Substrate 10 minutes with mega sonic wave, available organic solvent has but is not limited to absolute ethyl alcohol, acetone, isopropyl alcohol, CCl
4Deng, preferred organic is an isopropyl alcohol, and the megasonic frequency of employing is not less than 100kHz, and preferred megasonic frequency is 1MHz, and the Sapphire Substrate after cleaning with organic solvent adopts spray, overflow mode to clean 15 minutes with electron-grade water.
In order to remove the inorganic metal contaminating impurity on Sapphire Substrate surface, adopt multiple tracks to clean step by step, cleaning step is following:
(1) uses NH
3H2O: H
2O
2: H
2O=1: 1: 3～8 mixed liquor cleaned 10 minutes Sapphire Substrate, and preferred mixed liquor is NH
3H
2O: H
2O
2: H
2O=1: 1: 5, cleaning temperature was 20 ℃～90 ℃, and preferred cleaning temperature is 80 ℃, NH in the cleaning fluid
4 +With the heavy metal ion generation complex reaction of substrate surface, generate soluble metal salt and remove;
(2) Sapphire Substrate is through NH
3H
2O, H
2O
2And H
2After the O mixed liquor cleans, cleaned 15 minutes with the mode of spray, overflow with electron-grade water, thoroughly to remove heavy metal complex;
(3) use HCl: H
2O
2: H
2O=1: 1: 3～8 mixed liquor cleaned 10 minutes Sapphire Substrate, and preferred mixed liquor is HCl: H
2O
2: H
2O=1: 1: 5, cleaning temperature was 20 ℃～90 ℃, and preferred cleaning temperature is 80 ℃, the H in the cleaning fluid
+With light metal impurity generation displacement reaction, generate the salt of solubility and remove;
(4) Sapphire Substrate is through HCl, H
2O
2And H
2After the O mixed liquor cleans, with electron-grade water with spray, the mode of overflow 15 minutes, thoroughly to remove metal ion;
(5) use H
2SO
4And H
3PO
4Mixed liquor Sapphire Substrate was cleaned 10 minutes H
2SO
4And H
3PO
4The ratio of mixed liquor be 1: 2～4, preferred H
2SO
4And H
3PO
4The ratio of mixed liquor be H
2SO
4: H
3PO
4=1: 3, this mixed liquor can be removed the oxide layer of Sapphire Substrate, and cleaning temperature is 150 ℃～350 ℃, and preferred cleaning temperature is 250 ℃.
(6) Sapphire Substrate is through H
2SO
4And H
3PO
4The substrate that cleans of mixed liquor with electron-grade water with spray, the mode of overflow cleaned 15 minutes, thoroughly to remove H
2SO
4And H
3PO
4Residual;
3, dry through the Sapphire Substrate of above-mentioned cleaning step or with the N of 6N
2After drying up, be positioned over the Ecr plasma that is equipped with refletcion high-energy electron diffraction appearance (RHEED) and strengthen in metal organic chemical vapor deposition (ECR-PEMOCVD) device, feed the N of 6N
2And H
2Gaseous mixture clean.N in this step cleaning process
2Flow 30～200sccm, preferred N
2Flow 100sccm, H
2Flow is 0.2～2sccm, preferred H
2Flow 1sccm, scavenging period are 10～30 minutes, and preferred scavenging period is 15 minutes.Through the cleaning of this step, substrate surface non-oxidation layer, no surface damage and sub-surface damage layer, substrate surface nitrogenize.
The invention has the beneficial effects as follows: utilize cleaning method of the present invention, substrate surface non-oxidation layer, no surface damage, no sub-surface damage, there is not Al in substrate surface because of nitridation reaction takes place
3 +Outstanding key can not caught airborne contaminant particles, and the product yield that is used to do the PSS substrate or directly carry out the GaN hetero-epitaxy all is improved.
The specific embodiment
Embodiment
A kind of cleaning method of Sapphire Substrate is after the Sapphire Substrate process is removed organic impurities and the cleaning of inorganic metal impurity, passes through the cleaning of hydrogen nitrogen plasma again, may further comprise the steps:
(1), Sapphire Substrate is positioned over uses frequency to clean 10 minutes in the pure isopropyl alcohol of electronics as the mega sonic wave of 1MHz;
(2), the Sapphire Substrate sheet after with electron-grade water step (1) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(3), use NH
3H
2O: H
2O
2: H
2O=1: the Sapphire Substrate after 1: 5 mixed liquor cleans step (2) was cleaned 10 minutes, and cleaning temperature is 80 ℃;
(4), the Sapphire Substrate sheet after with electron-grade water step (3) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(5), use HCl: H
2O
2: H
2O=1: the Sapphire Substrate after 1: 5 mixed liquor cleans step (4) was cleaned 10 minutes, and cleaning temperature is 80 ℃;
(6), the Sapphire Substrate sheet after with electron-grade water step (5) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(7), use H
2SO
4: H
3PO
4Sapphire Substrate after=1: 3 mixed liquor cleans step (6) was cleaned 10 minutes, and cleaning temperature is 250 ℃;
(8), the Sapphire Substrate sheet after with electron-grade water step (7) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(9), with the N of 6N
2Sapphire Substrate sheet after gas cleans step (8) dries in the drier machine, dries up;
(10), the Sapphire Substrate sheet that cleans through step (9) is positioned over the Ecr plasma that is equipped with refletcion high-energy electron diffraction appearance (RHEED) and strengthens in metal organic chemical vapor deposition (ECR-PEMOCVD) device N of feeding 6N
2And H
2Gaseous mixture clean N
2Flow 100sccm, H
2Flow 1sccm, scavenging period are 15 minutes.
Cleaning through this technology; Sapphire Substrate after cleaning is done LPD-ICPMS detection substrate surface oxide layer and metal impurities and high-resolution TEM respectively detected surface damage, sub-surface damage; Testing result shows, through the Sapphire Substrate surface non-oxidation layer of this invention cleaning, no surface damage and sub-surface damage layer.
What describe in the above specification is the specific embodiment of the present invention; Various not illustrating constitutes restriction to flesh and blood of the present invention; Under the those of ordinary skill of technical field after having read specification can to before the described specific embodiment make an amendment or be out of shape, and do not deviate from essence of an invention and scope.
Claims (4)
1. the cleaning method of a Sapphire Substrate is after the Sapphire Substrate process is removed organic impurities and the cleaning of inorganic metal impurity, passes through the cleaning of hydrogen nitrogen plasma again, it is characterized in that may further comprise the steps:
(1) Sapphire Substrate is positioned in the pure organic solvent of electronics with mega sonic wave cleaning 10 minutes;
(2) the Sapphire Substrate sheet after with electron-grade water step (1) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(3) use NH
3H
2O: H
2O
2: H
2O=1: the Sapphire Substrate after 1: 3～8 mixed liquor cleans step (2) was cleaned 10 minutes;
(4) the Sapphire Substrate sheet after with electron-grade water step (3) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(5) use HCl: H
2O
2: H
2O=1: the Sapphire Substrate after 1: 3～8 mixed liquor cleans step (4) was cleaned 10 minutes;
(6) the Sapphire Substrate sheet after with electron-grade water step (5) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(7) use H
2SO
4And H
3PO
4The Sapphire Substrate of mixed liquor after step (6) is cleaned cleaned 10 minutes;
(8) the Sapphire Substrate sheet after with electron-grade water step (7) being cleaned cleaned 15 minutes with the mode of spray, overflow;
(9) with the N of 6N
2Sapphire Substrate sheet after gas cleans step (8) dries in the drier machine, dries up.
(10) the Sapphire Substrate sheet that cleans through step (9) is positioned over the Ecr plasma that is equipped with refletcion high-energy electron diffraction appearance RHEED to be strengthened in the metal organic chemical vapor deposition ECR-PEMOCVD device, feeds the N of 6N
2And H
2Gaseous mixture clean.
2. the cleaning method of a kind of Sapphire Substrate as claimed in claim 1 is characterized in that: H in the described step (7)
2SO
4And H
3PO
4The ratio of mixed liquor be 1: 2～4;
3. the cleaning method of a kind of Sapphire Substrate as claimed in claim 1, it is characterized in that: the cleaning temperature in the described step (7) is 150 ℃～350 ℃.
4. the cleaning method of a kind of Sapphire Substrate as claimed in claim 1 is characterized in that: N in the described step (10)
2Flow is 30～200sccm, H
2Flow is 0.2～2sccm, and scavenging period is 10～30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101019843A CN102632055A (en) | 2012-03-31 | 2012-03-31 | Method for cleaning sapphire substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101019843A CN102632055A (en) | 2012-03-31 | 2012-03-31 | Method for cleaning sapphire substrate |
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|---|---|---|---|
| CN2012101019843A Pending CN102632055A (en) | 2012-03-31 | 2012-03-31 | Method for cleaning sapphire substrate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962226A (en) * | 2012-12-06 | 2013-03-13 | 江苏吉星新材料有限公司 | Method for cleaning polished sapphire substrate wafer |
| CN103021833A (en) * | 2012-12-21 | 2013-04-03 | 中国科学院半导体研究所 | Method for reducing concentration of residual impurities on surface of substrate |
| CN103111434A (en) * | 2013-01-15 | 2013-05-22 | 安徽康蓝光电股份有限公司 | Final cleaning technique in sapphire processing |
| CN103521474A (en) * | 2013-08-20 | 2014-01-22 | 曾锡强 | Method for cleaning surfaces of sapphire substrate materials by using polishing to replace washing |
| CN104259133A (en) * | 2014-07-31 | 2015-01-07 | 江苏吉星新材料有限公司 | Cleaning process of sapphire wafer before annealing |
| CN105903694A (en) * | 2016-04-27 | 2016-08-31 | 上海超硅半导体有限公司 | Cleaning method and back-side defect reworking method for large-size sapphire substrate before annealing |
| CN106206279A (en) * | 2016-07-28 | 2016-12-07 | 常州亿晶光电科技有限公司 | A kind of chemically polishing method of sapphire filament wafer |
| CN105938793B (en) * | 2016-06-27 | 2019-02-26 | 山东浪潮华光光电子股份有限公司 | A kind of cleaning process for back plating wafer |
| CN111097748A (en) * | 2019-12-27 | 2020-05-05 | 北京理工大学 | Multi-element composite cleaning method for polished large-size sapphire window |
| CN111185432A (en) * | 2020-01-14 | 2020-05-22 | 江苏京晶光电科技有限公司 | Cleaning process for replacing acid cleaning of sapphire substrate wafer |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962226A (en) * | 2012-12-06 | 2013-03-13 | 江苏吉星新材料有限公司 | Method for cleaning polished sapphire substrate wafer |
| CN103021833A (en) * | 2012-12-21 | 2013-04-03 | 中国科学院半导体研究所 | Method for reducing concentration of residual impurities on surface of substrate |
| CN103111434A (en) * | 2013-01-15 | 2013-05-22 | 安徽康蓝光电股份有限公司 | Final cleaning technique in sapphire processing |
| CN103521474A (en) * | 2013-08-20 | 2014-01-22 | 曾锡强 | Method for cleaning surfaces of sapphire substrate materials by using polishing to replace washing |
| CN103521474B (en) * | 2013-08-20 | 2015-07-22 | 曾锡强 | Method for cleaning surfaces of sapphire substrate materials by using polishing to replace washing |
| CN104259133A (en) * | 2014-07-31 | 2015-01-07 | 江苏吉星新材料有限公司 | Cleaning process of sapphire wafer before annealing |
| CN105903694A (en) * | 2016-04-27 | 2016-08-31 | 上海超硅半导体有限公司 | Cleaning method and back-side defect reworking method for large-size sapphire substrate before annealing |
| CN105938793B (en) * | 2016-06-27 | 2019-02-26 | 山东浪潮华光光电子股份有限公司 | A kind of cleaning process for back plating wafer |
| CN106206279A (en) * | 2016-07-28 | 2016-12-07 | 常州亿晶光电科技有限公司 | A kind of chemically polishing method of sapphire filament wafer |
| CN111097748A (en) * | 2019-12-27 | 2020-05-05 | 北京理工大学 | Multi-element composite cleaning method for polished large-size sapphire window |
| CN111185432A (en) * | 2020-01-14 | 2020-05-22 | 江苏京晶光电科技有限公司 | Cleaning process for replacing acid cleaning of sapphire substrate wafer |
| CN111185432B (en) * | 2020-01-14 | 2021-03-19 | 江苏京晶光电科技有限公司 | Cleaning process for replacing acid cleaning of sapphire substrate wafer |
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Application publication date: 20120815 Assignee: Changzhou Tongtai Photoelectric Co., Ltd. Assignor: Jiangsu Xinheatai Machinery Group Contract record no.: 2013320000153 Denomination of invention: Method for cleaning sapphire substrate License type: Exclusive License Record date: 20130319 |
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Owner name: CHANGZHOU TONGTAI OPTOELECTRONIC CO., LTD. Free format text: FORMER OWNER: JIANGSU XINHETAI OPTOELECTRONIC TECHNOLOGY CO., LTD. Effective date: 20131112 |
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