CN1542917A - Method for growing p type zinc oxide crystal film by real-time nitrogen doping - Google Patents
Method for growing p type zinc oxide crystal film by real-time nitrogen doping Download PDFInfo
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- CN1542917A CN1542917A CNA2003101084716A CN200310108471A CN1542917A CN 1542917 A CN1542917 A CN 1542917A CN A2003101084716 A CNA2003101084716 A CN A2003101084716A CN 200310108471 A CN200310108471 A CN 200310108471A CN 1542917 A CN1542917 A CN 1542917A
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- purity
- zinc oxide
- crystal film
- nitrogen
- growing
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- 239000013078 crystal Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 66
- 239000011787 zinc oxide Substances 0.000 title claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 33
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 15
- 239000012159 carrier gas Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen 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
- 230000000802 nitrating effect Effects 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 29
- 239000010408 film Substances 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 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
- 125000004429 atom Chemical group 0.000 description 1
- 230000001276 controlling effect 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
- 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
- 230000002779 inactivation Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-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
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 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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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
This invention discloses a method for real-time doping N to grow p type ZnO crystal film which uses activated and cracked N source gas to generate N atoms including: cleaning the substrate surface to put it in a metal organic chemical vapor deposition growth chamber pumped to at least 104pa then to heat the substrate to 350-950deg.C and an O source and pure organic Zn source are input into the chamber by a carrier gas to grow ZnO film on the substrate with the Molar flow of 5~10000mm mol/min and 0.1~1000mm mol/min, at the same time N atoms separated from the N source gas is input to the chamber and the internal pressure is controlled at 0.01-100pa so as to prepare a P type ZnO crystal film with the doped concentration at 1.0x10 to the power 15cm[-3]~1.0x10 to the power 19cm[-3].
Description
Technical field
The present invention relates to the doping 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
Zinc oxide is as a kind of important semiconductor material with wide forbidden band, and it is in the optoelectronic areas great prospect.But realize the application of Zinc oxide-base device, the n with certain carrier concentration of growing controllable and p type zinc oxide crystal film 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 make zinc oxide crystal film prepare luminescent device, 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 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, the hole is not easy to thermal excitation and enters valence band, the solid solubility of acceptor doping is also very low, thereby is difficult to realize that the p type changes, and becomes 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 dopant, 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 high-purity nitrogen source gas of activation cracking that in the Organometallic Chemistry vapor deposition process, utilizes and produce the method that nitrogen-atoms carries out real-time doping nitrogen growing p-type zinc oxide crystal film.
The method of real-time doping nitrogen growing p-type zinc oxide crystal film of the present invention is that the Organometallic Chemistry gas deposition is that doped source realizes with the activation nitrogen-atoms, 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
-4Pa, heated substrate then, making underlayer temperature is 350～950 ℃, with high-purity oxygen source of purity＞99.999% and with high-purity carrier gas of purity＞99.999% with in high-purity organic zinc source input growth room of purity＞99.999% on substrate growing zinc oxide film, the molar flow of high-purity oxygen source and high-purity organic zinc source is respectively 5～100000 μ mol/min and 0.1～1000 μ mol/min, to activate the isolated nitrogen-atoms input of the high-purity nitrogen source gas growth room of cracking purity＞99.999% with atomic generator simultaneously, the control growing chamber internal pressure is 10
-2～100Pa, preparation nitrating concentration is 1.0 * 10
15Cm
-3～1.0 * 10
19Cm
-3P type zinc oxide crystal film.
Among the present invention, used atomic generator can be conventional electron cyclotron resonace atomic generator or radio frequency atomic generator, high-purity nitrogen source gas cracking is obtained nitrogen-atoms separate by atomic source disadvantageous other charged ion that mixes is realized.High-purity nitrogen source gas can be nitrogen or NH
3Or N
2Gases such as O.Generally making the atomic generator outlet and the distance of substrate is 4 to 20cm.
Above-mentioned high-purity organic zinc source can be diethyl zinc or zinc methide; High-purity oxygen source can be N
2O or high purity oxygen gas or water or the tert-butyl alcohol; High-purity carrier gas can be nitrogen or hydrogen or argon gas.Said substrate is silicon chip or sapphire or glass or zinc oxide.
The pressure of answering the control growing chamber in the thin film growth process is less than 100pa, in order to avoid atomic generator can't operate as normal, and the nitrogen-atoms that produces since with the collision of gas molecule inactivation.Can prepare different levels of doping p type zinc oxide crystal film by controlling the zinc source and flow, growth temperature and the pressure of oxygen source and the flow of nitrogen-atoms.
Advantage of the present invention:
1) the activity ratio height of the higher and nitrogen-atoms that mixes of doping content, because nitrogen is the form arrival substrate with atom, and the comparatively ideal energy that single nitrogen-atoms has, have enough energy on the one hand and be attached to the zinc-oxide film in the growth and replace oxygen atom, be not enough to damage the film crystal quality on the other hand again;
2) owing to the nitrogen that flows to substrate is to be activated the nitrogen-atoms that the cracking nitrogen source gas obtains, fall and other charged energetic ion is separated, so improved crystal mass to a great extent, and avoided these ions binding to form donor pair nitrogen in the crystal being subjected to main product to give birth to compensating action;
3) can realize real-time doping, in the zinc oxide crystal film growth course, realize simultaneously mixing;
4) doping content can be controlled by the flow of regulating growth for Thin Film speed and nitrogen-atoms;
5) can obtain directly applying to the high-quality p type of opto-electronic device zinc-oxide film;
6) better repeatability and stability are arranged.
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 radio frequency atomic generator; 2 is the growth room; 3 is organic zinc source carrier gas air inlet pipe; 4 is the nitrogenous source air inlet pipe; 5 is the oxygen source gas air inlet pipe; 6 is substrate; 7 specimen holders; 8 is substrate heater; 9 is exhaust outlet; 10 is rotary electric machine.
Embodiment
Further specify the present invention below in conjunction with instantiation.
Earlier silicon chip substrate is put on the specimen holder 7 of growth room 2 through after the surface clean, closed each air inlet then, suction to 10
-4Pa makes its temperature reach 450 ℃ by 8 pairs of substrate heating of substrate heater, will contain the nitrogen of high-purity (more than 99.999%) diethyl zinc, high-purity (more than 99.999%) N respectively from organic zinc source carrier gas air inlet pipe 3 and oxygen source gas air inlet pipe 5
2O feeds growth room 2, makes diethyl zinc and N
2The molar flow of O is 10 μ mol/min and 2000 μ mol/min respectively, and the indoor pressure of control growing is at 1Pa, simultaneously high-purity (more than 99.999%) nitrogen source gas one nitrogen is fed radio frequency atomic generator 1 from air inlet pipe 4, nitrogen flow is 2sccm, the effect to nitrogen by the radio frequency atomic generator produces nitrogen-atoms, nitrogen-atoms flows out and the arrival substrate from the radio frequency atomic generator, be attached to the lattice position of the oxygen atom in the zinc oxide crystal film in the growth, obtain carrier concentration and be about 1 * 10
18Cm
-3P type zinc oxide crystal film.
Adopt the present invention to grow and have the p type zinc-oxide film that crystal mass is better, doping content is higher, be used to prepare the Zinc oxide-base opto-electronic device.
Claims (7)
1. the method for real-time doping nitrogen growing p-type zinc oxide 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
-4Pa, heated substrate then, making underlayer temperature is 350～950 ℃, with high-purity oxygen source of purity＞99.999% and with high-purity carrier gas of purity＞99.999% with in high-purity organic zinc source input growth room of purity＞99.999% on substrate growing zinc oxide film, the molar flow of high-purity oxygen source and high-purity organic zinc source is respectively 5～100000 μ mol/min and 0.1～1000 μ mol/min, to activate the isolated nitrogen-atoms input of the high-purity nitrogen source gas growth room of cracking purity＞99.999% with atomic generator simultaneously, the control growing chamber internal pressure is 10
-2～100Pa, preparation nitrating concentration is 1.0 * 10
15Cm
-3～1.0 * 10
19Cm
-3P type zinc oxide crystal film.
2. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that used atomic generator is electron cyclotron resonace atomic generator or radio frequency atomic generator.
3. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that said organic zinc source is high-purity diethyl zinc or zinc methide.
4. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that said oxygen source can be a high-purity N
2O or NO or high purity oxygen gas or water or the tert-butyl alcohol.
5. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that said carrier gas can be high pure nitrogen or hydrogen or argon gas.
6. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that said high-purity nitrogen source gas with atomic generator activation cracking is nitrogen or NH
3Or N
2O gas.
7. the method for real-time doping nitrogen growing p-type zinc oxide crystal film according to claim 1 is characterized in that said substrate is silicon chip or sapphire or glass or zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108471 CN1258804C (en) | 2003-11-04 | 2003-11-04 | Method for growing p type zinc oxide crystal film by real-time nitrogen doping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108471 CN1258804C (en) | 2003-11-04 | 2003-11-04 | Method for growing p type zinc oxide crystal film by real-time nitrogen doping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1542917A true CN1542917A (en) | 2004-11-03 |
| CN1258804C CN1258804C (en) | 2006-06-07 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316076C (en) * | 2005-10-26 | 2007-05-16 | 浙江大学 | Process for Li-N codoping growth P type ZnO crystal film |
| CN100365889C (en) * | 2006-05-18 | 2008-01-30 | 中微光电子(潍坊)有限公司 | Method for preventing vertical-cavity-face emitting semiconductor laser from cracking while wet oxidation |
| CN100431970C (en) * | 2005-10-27 | 2008-11-12 | 江苏大学 | Method and device for preparing zinc oxide nano-crystal by microwave induced adulterant oxidation |
| CN103180491A (en) * | 2010-09-25 | 2013-06-26 | 叶志镇 | Method for preparing p-type zno-based material |
-
2003
- 2003-11-04 CN CN 200310108471 patent/CN1258804C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316076C (en) * | 2005-10-26 | 2007-05-16 | 浙江大学 | Process for Li-N codoping growth P type ZnO crystal film |
| CN100431970C (en) * | 2005-10-27 | 2008-11-12 | 江苏大学 | Method and device for preparing zinc oxide nano-crystal by microwave induced adulterant oxidation |
| CN100365889C (en) * | 2006-05-18 | 2008-01-30 | 中微光电子(潍坊)有限公司 | Method for preventing vertical-cavity-face emitting semiconductor laser from cracking while wet oxidation |
| CN103180491A (en) * | 2010-09-25 | 2013-06-26 | 叶志镇 | Method for preparing p-type zno-based material |
| CN103180491B (en) * | 2010-09-25 | 2016-02-17 | 叶志镇 | A kind of preparation method of p-type zno-based material |
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| Publication number | Publication date |
|---|---|
| CN1258804C (en) | 2006-06-07 |
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