CN1265434C - Method for preparing p type crystal film - Google Patents
Method for preparing p type crystal film Download PDFInfo
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- CN1265434C CN1265434C CN 200310108466 CN200310108466A CN1265434C CN 1265434 C CN1265434 C CN 1265434C CN 200310108466 CN200310108466 CN 200310108466 CN 200310108466 A CN200310108466 A CN 200310108466A CN 1265434 C CN1265434 C CN 1265434C
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- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011787 zinc oxide Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229960001296 zinc oxide Drugs 0.000 claims description 23
- 239000012159 carrier gas Substances 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910002601 GaN Inorganic materials 0.000 claims description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 238000001947 vapour-phase growth Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
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- Chemical Vapour Deposition (AREA)
Abstract
The present invention discloses a method for preparing a p type zinc oxide crystal thin film. The method has the following steps: the surface of a substrate is at first cleaned and the substrate is then arranged in a vapor phase deposition growth chamber for metal organic chemistry; the vacuum degree of the growth chamber is drawn to at least 10<-2> Pa and then the substrate is heated; the temperature of the substrate is controlled within 350 to 950 DEG C and the inner pressure of the growth chamber is controlled within the range of 10<-2> to 10000 Pa; a high-purity organic zinc source is input into the growth chamber by high-purity carrying gas and simultaneously, high-purity N2O and high-purity NO gas are input to the growth chamber; the molar flow rates of the organic zinc source, the N2O and the NO are respectively 0.1 to 1*10<3> mu mol/min, 1 to 1*10<5> mu mol/min and 1 to 1*10<5> mu mol/min; the zinc source and an oxygen source and a nitrogen source react and grow in the substrate to obtain the P type zinc oxide thin film with the doping density of 2.0*10<15> cm <-3> to 5.0*10<19> cm <-3> and the resistivity of 0.1 to 1*10<4> omega cm. The preparing method of the invention has the advantages of repeatability and high stability and a prepared p type zinc oxide thin film crystal has the advantages of high quality, good homogeneity, etc.
Description
Technical field
The present invention relates to the preparation method of p type zinc oxide crystal film.Be about in the Organometallic Chemistry gas deposition zinc oxide crystal film process specifically, the method for real-time doping nitrogen growing p-type zinc oxide crystal film.
Background technology
A kind of important semiconductor material with wide forbidden band of zinc oxide, energy gap is 3.3ev under its room temperature, is suitable for making royal purple light solid luminescence device and detector.But realize the application of ZnO base luminescent, the n type with certain carrier concentration and the p type zinc oxide crystal film of growing controllable are necessary.At present, people are relatively more abundant for the research of n type zinc oxide crystal film, the growth of the low-resistance n type zinc oxide crystal film of can realize in real time, concentration is controlled.But prepare ZnO base luminescent, must preparation zinc oxide p n knot.Because the defective that there are many intrinsic alms giver's defectives in zinc oxide and mix and cause, they can give birth to the height auto-compensation to being subjected to main product; And the zinc oxide acceptor level is dark (except the N) generally, and the hole is not easy to thermal excitation and enters valence band, and the solid solubility of acceptor doping is also very low, thereby is difficult to realize that the p type changes, and is to become the bottleneck that restriction zinc oxide is realized the exploitation luminescent device.The p type of zinc oxide crystal film mixes to study and also is in the incipient stage at present, and concentration is controlled, and the p type zinc-oxide film of good reproducibility also is difficult to realize.
The doping of bibliographical information p type zinc oxide crystal film at present mainly contains four kinds of methods: (1) utilizes highly active nitrogen as the dopant nitrating, the codope of (2) gallium and nitrogen, and (3) mix arsenic, and (4) mix phosphorus.The concrete method for preparing zinc oxide thin film that wherein uses only limits to methods such as molecular beam epitaxy, pulsed laser deposition, magnetron sputtering and diffusion, and these methods are owing to reasons such as the quality of material, preparation cost make their industrial utilization be worth not high.
Summary of the invention
The purpose of this invention is to provide a kind of higher NO of activity that in the Organometallic Chemistry vapor deposition process, utilizes and carry out real-time doping nitrogen, add N simultaneously as nitrogen source gas
2O suppresses the generation of intrinsic defect, the method for the p type zinc oxide crystal film that growth resistance is controlled.
The method for preparing p type zinc oxide crystal film of the present invention, step is as follows: put into Organometallic Chemistry gas deposition growth room after earlier substrate surface being cleaned, growth room's vacuum degree is extracted at least 10
-2Pa, heated substrate then, making underlayer temperature is 350～950 ℃, the control growing chamber internal pressure is 10
-2In-10000Pa the scope, in high-purity carrier gas of purity＞99.999% high-purity organic zinc source input growth room, simultaneously with the high-purity N of purity＞99.9% with purity＞99.999%
2The high-purity N O gas input growth room of O and purity＞99%, organic zinc source, N
2The molar flow of O and NO is respectively 0.1～1 * 10
3μ mol/min, 1～1 * 10
5μ mol/min and 1～1 * 10
5μ mol/min, zinc source, oxygen source and nitrogenous source are in substrate reaction growth, and obtaining doping content is 2.0 * 10
15Cm
-3-5.0 * 10
19Cm
-3, resistivity is 0.1-1 * 10
4The p type zinc-oxide film of Ω cm.
Above-mentioned organic zinc source can be diethyl zinc or zinc methide; Carrier gas can be nitrogen or hydrogen or argon gas; Said substrate is silicon chip or sapphire or glass or zinc oxide or gallium nitride or carborundum.
Used high-purity N simultaneously in the growing p-type zinc oxide crystal film process of the present invention
2Two kinds of gases of O and NO, ZnO film are grown required oxygen source by N
2Oxygen atom among O and the NO provides jointly, and the p type of film mix required nitrogenous source by the nitrogen-atoms among the NO for providing.N
2Feed the growth room again after two kinds of gases of O and NO can mix, also can feed the growth room respectively, mix again in the growth room.N
2O and NO can also use N
2, H
2Or Ar is diluted the back use.
Its nitrating principle is that the lower and active NO gas of nitrogen-oxygen bond binding energy can provide nitrogenous source and oxygen source is provided for reaction, simultaneously N
2The reaction that exists for of O gas provides enough oxygen, thereby suppressed the formation in oxygen room and zinc gap, and oxygen room and zinc gap all are the alms givers, electronics are provided, and therefore reduce these two kinds of intrinsic defects and have just reduced their compensation to the hole, have improved the valid density in hole.The concentration in hole can be by regulating NO and N in addition
2The doping of nitrogen in the proportioning of O and the flow size control film, thereby the size of the resistivity of adjusting film.
Preparation method of the present invention has repeatability and good stability, the p type zinc-oxide film crystal mass height that makes, advantages such as good uniformity.
Description of drawings
Fig. 1 is the Organometallic Chemistry vapor deposition apparatus schematic diagram that adopts according to the inventive method.
Among the figure: 1 is the growth room; 2 is organic zinc source carrier gas air inlet pipe; 3 is NO and N
2The O air inlet pipe; 4 is substrate heater; 5 is rotary electric machine; 6 is exhaust outlet; 7 is specimen holder; 8 is substrate.
Embodiment
Further specify the present invention below in conjunction with instantiation.
Earlier Sapphire Substrate is put on the reative cell specimen holder 7 through after the surface clean, closed each air inlet then, suction to 10
-2Pa makes its temperature reach 450 ℃ by 4 pairs of substrate heating of substrate heater, will contain nitrogen, the high-purity N of high-purity diethyl zinc (purity＞99.999%) respectively from air inlet pipeline 2,3
2O (purity＞99.9%) and NO (purity＞99%) feed growth room 1, make diethyl zinc, NO and N
2The molar flow of O is 10 μ mol/min, 2000 μ mol/min and 1000 μ mol/min respectively, and the pressure of keeping in the growth room makes it be controlled in 100Pa, and reactant is in substrate surface reactions, and obtaining doping content is 1.2 * 10
18Cm
-3, resistivity is about 10 Ω cm, and crystal mass is p type zinc-oxide film preferably.
Claims (4)
1. method for preparing p type ZnO crystal film is characterized in that step is as follows: put into Organometallic Chemistry gas deposition growth room after earlier will substrate surface cleaning, growth room's vacuum degree is extracted at least 10
-2Pa, heated substrate then, making underlayer temperature is 350～950 ℃, the control growing chamber internal pressure is 10
-2In-10000Pa the scope, in high-purity carrier gas of purity＞99.999% high-purity organic zinc source input growth room, simultaneously with the high-purity N of purity＞99.9% with purity＞99.999%
2The high-purity N O gas input growth room of O and purity＞99%, organic zinc source, N
2The molar flow of O and NO is respectively 0.1～1 * 10
3μ mol/min, 1～1 * 10
5μ mol/min and 1～1 * 10
5μ mol/min, zinc source, oxygen source and nitrogenous source are in substrate reaction growth, and obtaining doping content is 2.0 * 10
15Cm
-3-5.0 * 10
19Cm
-3, resistivity is 0.1-1 * 10
4The p type zinc-oxide film of Ω cm, above-mentioned organic zinc source is diethyl zinc or zinc methide.
2. the method for preparing p type ZnO crystal film according to claim 1 is characterized in that said carrier gas is nitrogen or hydrogen or argon gas.
3. the method for preparing p type ZnO crystal film according to claim 1 is characterized in that N
2O and NO can use N
2, H
2Or Ar is diluted the back use.
4. the method for preparing p type ZnO crystal film according to claim 1 is characterized in that used substrate is silicon chip or sapphire or glass or ZnO or gallium nitride or carborundum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108466 CN1265434C (en) | 2003-11-04 | 2003-11-04 | Method for preparing p type crystal film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108466 CN1265434C (en) | 2003-11-04 | 2003-11-04 | Method for preparing p type crystal film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1542916A CN1542916A (en) | 2004-11-03 |
| CN1265434C true CN1265434C (en) | 2006-07-19 |
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ID=34334686
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310108466 Expired - Fee Related CN1265434C (en) | 2003-11-04 | 2003-11-04 | Method for preparing p type crystal film |
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| Country | Link |
|---|---|
| CN (1) | CN1265434C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328418C (en) * | 2005-10-26 | 2007-07-25 | 浙江大学 | Process for Li doping growing P type ZnO Single Crystal film |
| CN1316076C (en) * | 2005-10-26 | 2007-05-16 | 浙江大学 | Process for Li-N codoping growth P type ZnO crystal film |
| CN100353578C (en) * | 2005-11-18 | 2007-12-05 | 浙江大学 | UV electroluminescence device of silicon base zinc oxide and preparation process thereof |
| ES2374744T3 (en) * | 2006-09-08 | 2012-02-21 | Pilkington Group Limited | LOW TEMPERATURE PROCEDURE FOR MANUFACTURING AN ITEM COATED WITH ZINC OXIDE. |
| CN101311364B (en) * | 2008-03-10 | 2010-12-15 | 中国科学院长春光学精密机械与物理研究所 | Process for preparing P-shaped zinc oxide semiconductor bulk material |
| CN114182235B (en) * | 2020-09-14 | 2023-09-29 | 北京环境特性研究所 | Method for establishing gas balance flow field in growth chamber |
-
2003
- 2003-11-04 CN CN 200310108466 patent/CN1265434C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1542916A (en) | 2004-11-03 |
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