CN1391259A - Process for growing P-type ZnO crystal film by real-time doping nitrogen - Google Patents
Process for growing P-type ZnO crystal film by real-time doping nitrogen Download PDFInfo
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- CN1391259A CN1391259A CN 02136110 CN02136110A CN1391259A CN 1391259 A CN1391259 A CN 1391259A CN 02136110 CN02136110 CN 02136110 CN 02136110 A CN02136110 A CN 02136110A CN 1391259 A CN1391259 A CN 1391259A
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- crystal film
- doping
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000013078 crystal Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A process for growing P-type ZnO crystal film by real-time doping of nitrogen includes washing substrate, putting it in reaction chamber of sputter equipment, vacuumizing heating, substrate to 200-600 deg.c, introducing the mixture of high-purity NH3 and O2, and sputter growing with high-purity Zn as target under 1-10 MPa.
Description
Technical Field
The invention relates to a doping method of p-type ZnO. In particular to a method for growing a p-type ZnO crystal film by real-time nitrogen doping.
Background
To realize the application of ZnO-based devices, the preparation of controllable n-type and p-type ZnO crystal films is necessary. At present, people have more sufficient research on n-type ZnO crystal films, and the growth of the low-resistance n-type ZnO crystal films with controllable concentration in real time can be realized by doping III-valence elements. But the ZnO crystal film is required to be prepared into a photoelectronic deviceThe ZnO pn junction must be prepared. Due to the existence of many intrinsic donor defects in ZnO, such as interstitial ZniAnd vacancy oxygen VOThe energy levels of the ZnO acceptor are respectively positioned at the bottom of the conduction band by 0.05eV and 0.3eV, the ZnO acceptor has a high self-compensation effect on the acceptor, the energy level of the ZnO acceptor is generally very deep (except for N), holes are not easy to be thermally excited to enter a valence band, and the solid solubility of acceptor doping is also very low, so that p-type conversion is difficult to realize, and the bottleneck for restricting ZnO from realizing industrialization is formed. At present, the p-type doping research of the ZnO crystal film is still in the beginning stage, and the p-type ZnO film with controllable concentration and good repeatability is difficult to realize.
The literature reports that there are four main methods for doping p-type ZnO crystal films: (1) the preparation method comprises the following steps of (1) utilizing high-activity nitrogen as a dopant, (2) co-doping gallium and nitrogen, (3) doping arsenic, and (4) doping phosphorus. The latter two have poor doping effect and toxicity to arsenic and phosphorus due to their deep acceptor level and low solid solubility. The former two methods use high-activity nitrogen doping and gallium and nitrogen co-doping, and because the activity of nitrogen is very low and the atomic radius is larger than that of oxygen atoms, the Chemical Vapor Deposition (CVD) and Molecular Beam Epitaxy (MBE) growth technologies are adopted, so that the position of the oxygen atoms is difficult to replace, and real-time controllable nitrogen doping cannot be realized.
Disclosure of Invention
The invention aims to provide a method for growing a p-type ZnO crystal thin film by real-time nitrogen doping.
The method for growing the p-type ZnO crystal film by real-time nitrogen doping adopts a magnetron sputtering method, firstly, the surface of a substrate is cleaned and then is placed into a reaction chamber of a direct-current reaction magnetron sputtering device, and the vacuum degree of the reaction chamber is pumped to at least 10-3Pa, heating the substrate to 200-600 deg.C, preferably 400-550 deg.C, and adding high-purity ammonia NH3(more than 99.99%) and high purity oxygen O2(more than 99.99 percent) is sputtering gas, the two gases are respectively controlled by a flow meter to enter a buffer chamber of the device, are fully mixed in the buffer chamber and then are introduced into a vacuum reaction chamber, and sputtering growth is carried out by taking high-purity Zn (more than 99.99 percent) as a target under the pressure of 1-10 Pa, wherein the partial pressure of ammonia and oxygenThe ratio is adjusted according to the doping concentration. According to NH3And O2Different voltage division ratios can prepare p-type ZnO crystal films with different doping concentrations, and the growth time is determined by the required thickness.
The substrate may be silicon or sapphire or glass.
The invention has the advantages that:
1) real-time doping can be realized, and doping is realized simultaneously in the growth process of the ZnO crystal film;
2) the doping concentration is higher due to NH3Is ionized during sputtering, nitrogen atoms are activated, and NH is generated3Has an ionization energy lower than N2Therefore, the doping efficiency of N is higher;
3) the doping concentration can be adjusted by adjusting the input NH3∶O2Controlling different partial pressure ratios;
4) has better repeatability and stability.
Drawings
The attached figure is a schematic diagram of a direct-current reaction magnetron sputtering device adopted by the method
In the figure, 1 and 2 are respectively an ammonia gas inlet pipeline and an oxygen gas inlet pipeline; 3 is a flowmeter; 4 a buffer chamber; 5, a sample rack; 6, a heater; 7, a vacuum gauge; 8, an automatic pressure controller; 9S gun
Detailed Description
The invention is further illustrated below with reference to specific examples.
Firstly, the substrate is placed on a reaction chamber sample frame 5 after the surface of the substrate is cleaned, the substrate is placed downwards, the contamination of granular impurities to the substrate is effectively prevented, and the vacuum degree of the reaction chamber is pumped to 10-3Pa; heating the substrate by using a heater, wherein the temperature of the substrate is controlled at 500 ℃; the sputtering gas is high-purity NH3(99.99% or more) and high-purity O2(more than 99.99%) two-way gasThe mixture enters a buffer chamber 4 through air inlet pipes 1 and 2, and is introduced into a vacuum chamber after being fully mixed in the buffer chamber, the pressure in the vacuum chamber is controlled by an automatic pressure controller 8, and the pressure is about 5 Pa. NH (NH)3And O2The partial pressure ratio can be adjusted at will by means of a flow meter 3, in this case NH, according to the doping requirements3∶O21: 1; sputtering growth is carried out by taking high-purity Zn (99.99%) on the S gun 9 as a target. The sputtering power is 32W for a certain time, and about 2 microns can be sputtered in half an hour. By regulating the input NH3∶O2The p-type ZnO crystal film with controllable doping concentration can be obtained by the partial pressure ratio.
The chemical reactions that occur during growth are as follows:
Claims (3)
1. A method for growing p-type ZnO crystal film by real-time doping nitrogen features that the magnetron sputtering method is used, the substrate surface is cleaned and then put in the reaction chamber of DC reaction magnetron sputtering equipment, and the vacuum degree in the reaction chamber is at least 10-3Pa, heating the substrate to enable the temperature ofthe substrate to be 200-600 ℃, taking high-purity ammonia gas and high-purity oxygen gas as sputtering gases, controlling the buffer chamber of the input device by a flow meter, fully mixing the two gases in the buffer chamber, introducing the mixture into a vacuum reaction chamber, and carrying out sputtering growth by taking high-purity Zn as a target material under the pressure of 1-10 Pa, wherein the partial pressure ratio of the ammonia gas to the oxygen gas is adjusted according to the doping concentration.
2. The method for growing the p-type ZnO crystal film by real-time nitrogen doping according to claim 1, wherein the temperature of the substrate is 400-550 ℃.
3. The method of growing p-type ZnO crystal film by real-time nitrogen doping according to claim 1, wherein the substrate is silicon or sapphire or glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136110 CN1206703C (en) | 2002-07-17 | 2002-07-17 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136110 CN1206703C (en) | 2002-07-17 | 2002-07-17 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
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| Publication Number | Publication Date |
|---|---|
| CN1391259A true CN1391259A (en) | 2003-01-15 |
| CN1206703C CN1206703C (en) | 2005-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02136110 Expired - Fee Related CN1206703C (en) | 2002-07-17 | 2002-07-17 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
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| Country | Link |
|---|---|
| CN (1) | CN1206703C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293606C (en) * | 2004-09-30 | 2007-01-03 | 浙江大学 | Method or growing N-Al co-blended p type ZnO transistor film by two step method |
| CN1327042C (en) * | 2005-03-28 | 2007-07-18 | 中国科学院半导体研究所 | Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer |
| CN100353578C (en) * | 2005-11-18 | 2007-12-05 | 浙江大学 | UV electroluminescence device of silicon base zinc oxide and preparation process thereof |
| CN100540756C (en) * | 2007-10-18 | 2009-09-16 | 中国科学院长春光学精密机械与物理研究所 | The method for preparing p type zinc-oxide film with n type zinc oxide |
| CN102002667A (en) * | 2010-11-22 | 2011-04-06 | 烟台睿创微纳技术有限公司 | Method and equipment for preparing high-repeatability vanadium oxide film |
| CN101599363B (en) * | 2009-04-09 | 2011-11-23 | 上海工程技术大学 | Preparation method of nitrogen-doped zinc oxide p-type diluted magnetic semiconductor material |
| CN101496117B (en) * | 2006-07-28 | 2012-04-18 | 株式会社爱发科 | Method for forming transparent conductive film |
| CN101405427B (en) * | 2006-03-17 | 2012-07-18 | Jx日矿日石金属株式会社 | Zinc oxide-based transparent conductor and sputtering target for forming the transparent conductor |
-
2002
- 2002-07-17 CN CN 02136110 patent/CN1206703C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293606C (en) * | 2004-09-30 | 2007-01-03 | 浙江大学 | Method or growing N-Al co-blended p type ZnO transistor film by two step method |
| CN1327042C (en) * | 2005-03-28 | 2007-07-18 | 中国科学院半导体研究所 | Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer |
| CN100353578C (en) * | 2005-11-18 | 2007-12-05 | 浙江大学 | UV electroluminescence device of silicon base zinc oxide and preparation process thereof |
| CN101405427B (en) * | 2006-03-17 | 2012-07-18 | Jx日矿日石金属株式会社 | Zinc oxide-based transparent conductor and sputtering target for forming the transparent conductor |
| CN101496117B (en) * | 2006-07-28 | 2012-04-18 | 株式会社爱发科 | Method for forming transparent conductive film |
| TWI423932B (en) * | 2006-07-28 | 2014-01-21 | Ulvac Inc | Film forming method of a transparent electroconductive film |
| CN100540756C (en) * | 2007-10-18 | 2009-09-16 | 中国科学院长春光学精密机械与物理研究所 | The method for preparing p type zinc-oxide film with n type zinc oxide |
| CN101599363B (en) * | 2009-04-09 | 2011-11-23 | 上海工程技术大学 | Preparation method of nitrogen-doped zinc oxide p-type diluted magnetic semiconductor material |
| CN102002667A (en) * | 2010-11-22 | 2011-04-06 | 烟台睿创微纳技术有限公司 | Method and equipment for preparing high-repeatability vanadium oxide film |
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| Publication number | Publication date |
|---|---|
| CN1206703C (en) | 2005-06-15 |
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