CN1772975A - Process for Li doping growing P type ZnO Single Crystal film - Google Patents
Process for Li doping growing P type ZnO Single Crystal film Download PDFInfo
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- CN1772975A CN1772975A CN 200510061274 CN200510061274A CN1772975A CN 1772975 A CN1772975 A CN 1772975A CN 200510061274 CN200510061274 CN 200510061274 CN 200510061274 A CN200510061274 A CN 200510061274A CN 1772975 A CN1772975 A CN 1772975A
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- crystal film
- type zno
- reaction chamber
- doping
- zno crystal
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- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims abstract description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000001989 lithium alloy Substances 0.000 claims abstract description 4
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 2
- 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
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000013077 target material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 22
- 239000011701 zinc Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000255 optical extinction spectrum Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram 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
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
The present invention discloses a method for growing Li-doped p-type ZnO crystal film. Said method is a magnetron sputtering method, and includes the following steps: cleaning substrate, placing the substrate in a reaction chamber of a direct-current reaction magnetron sputtering equipment, evacuating the reaction chamber, using zinc-lithium alloy as target material, using O2 and Ar as sputtering atmosphere, making sputtering growth at pressure of 3-5 Pa and 400-600 deg.C, after the growth is completed, annealing the film under the Ar atmosphere.
Description
Technical field
The present invention relates to p type ZnO crystal growth for Thin Film method, the especially method of Li doping growing P type ZnO crystal film.
Background technology
Preparing controlled n type and p type ZnO electrically conducting transparent crystal film is to realize zno-based photoelectric device key in application.At present, people for the research of n type ZnO crystal film relatively fully by donor elements such as doped with Al, Ga, In, can realize having the real-time doped growing of the n type ZnO crystal film of excellent properties.Yet the p type of ZnO mixes and but runs into many difficulties, and this mainly is that acceptor level is generally very dark, and ZnO itself exists many intrinsic alms giver's defectives (as gap zinc Zn because the solid solubility of acceptor doping element in ZnO is very low
iWith room oxygen V
O), to being subjected to the main self compensation effect that can produce height.The real-time doping that how to realize having the p type ZnO film of excellent properties has become a bottleneck of present restriction zno-based photoelectric device development.
The doped element of the p-ZnO that reports all concentrates on V group element in the world at present, and for example N, P, As etc. wherein mix the most general with N again.But V group element mixes and also has some problems: low such as the solid solubility of being led, acceptor level is darker, and the repeatability and the stability of the conduction of p type are not high.Then there is dispute for the I family adulterated feasibility of recipient element.Different Theoretical Calculation provides the result of contradiction, and the experiment aspect does not also realize the report of p-ZnO by I family element doping.Therefore the problem of being led for p-ZnO the best for which kind of element does not also have final conclusion.
Summary of the invention
The objective of the invention is provides the method for Li doping growing P type ZnO crystal film for overcoming the above-mentioned V group element existing problem of mixing.
The method of Li doping growing P type ZnO crystal film, employing be magnetron sputtering method, may further comprise the steps:
To put into the reaction chamber of direct current reaction magnetron sputtering device after the substrate cleaning, reaction chamber vacuum tightness is evacuated to and is higher than 5 * 10
-3Pa is that 0.1～1% zinc lithium alloy is a target with the lithium molar content, with purity oxygen and pure Ar as sputtering atmosphere, with two kinds of gases respectively by mass flowmeter control input buffering chamber, O
2: Ar=1: 2～2: 1, behind the surge chamber thorough mixing, introduce vacuum reaction chamber, under 3～5Pa pressure, underlayer temperature is 400～600 ℃, carries out sputter growth, the growth ending rear film 2～5min that under Ar atmosphere, anneals, annealing temperature is 450～550 ℃.
The purity of above-mentioned pure oxygen is more than 99.99%, and the purity of Ar is more than 99.99%.Said substrate can be silicon or sapphire or quartz or glass.
The present invention is with O
2As oxygen source, Ar is as auxiliary sputtering atmosphere.Sputter procedure, sputtered atom (containing Zn, Li atom) under the protection of Ar with O
2React, deposition generates Li doped p type ZnO crystal film on substrate.
Li content and O in the target
2Regulate according to doping content with the intrinsic standoff ratio of Ar, growth time is determined by required film thickness.Follow-up Ar protection annealing can improve the electrical properties of film effectively.Beneficial effect of the present invention is: method is simple, O in content that p type doping content can be by regulating Li in the target and the growth atmosphere
2: the different dividing potential drops of Ar are recently controlled; In the ZnO crystal thin film growth process, can realize being subjected to the real-time doping of main Li; Because doped element from target, therefore can realize high-concentration dopant; The present invention mixes with V group element and compares, and mixing with metal Li ion substitution has more shallow acceptor level, and the p-ZnO film that makes has good electric property, and is repeated and stable.
Description of drawings
Fig. 1 is the direct current reaction magnetron sputtering device synoptic diagram that adopts according to the inventive method.1 and 2 are respectively O among the figure
2Admission passage with Ar; 3 is mass flowmeter; 4 is surge chamber; 5 is specimen holder; 6 is well heater; 7 is vacuumometer; 8 is from the dynamic pressure controller; 9 is the S rifle; 10 is baffle plate; 11 is gas introduction tube;
Fig. 2 is x ray diffraction (XRD) collection of illustrative plates of the p type ZnO crystal film that makes of embodiment;
Fig. 3 is the optical transmission spectrum of the p type ZnO crystal film that makes of embodiment.
Embodiment
The present invention is further illustrated by example below in conjunction with accompanying drawing.
Will quartz substrate put on the reaction chamber specimen holder 5 after cleaning, substrate is desired the deposition table placed face down, can effectively prevent granular impurity to the staining of substrate, and reaction chamber vacuum tightness is evacuated to 1 * 10
-3Pa is that 1% zinc lithium alloy is a target with the lithium molar content, target is placed on the S rifle 9, with the O of purity 99.99%
2With the Ar of purity 99.99% as sputtering atmosphere, two kinds of gases are entered surge chamber 4 through inlet pipe 1 and 2 respectively, introduce vacuum reaction chamber by gas introduction tube 11 behind the surge chamber thorough mixing, the pressure in the vacuum chamber is by controlling from dynamic pressure controller 8, and pressure is 4Pa.O
2With the Ar intrinsic standoff ratio according to the doping needs, can regulate by under meter 3, this example is O
2: Ar=1: 1, under the sputtering power of 36W, begin sputter procedure, underlayer temperature is 550 ℃, growth time is 30min, the thick 350nm that is about of film.The growth ending rear film 2min that anneals under Ar atmosphere, annealing temperature is 500 ℃
The Li doped p type ZnO crystal film that makes has excellent room temperature electric property, and resistivity is 2.89 Ω cm, and hole concentration reaches 1.13 * 10
18Cm
-3, hall mobility is 1.91cm
2/ V.s.And electric property does not have considerable change after placing several months.
X ray diffraction (XRD) collection of illustrative plates of above-mentioned film is seen Fig. 2, has only ZnO (002) and two times of diffraction peaks thereof to occur, and shows that the Li doped p type ZnO crystal film that the inventive method makes has good crystal property;
Shown in Figure 3 is the optical transmission spectrum of above-mentioned film.As seen from the figure, about the transmissivity of visible region is up to 90%, a precipitous basic absorption limit is arranged at the 390nm place, show that the Li doped p type ZnO crystal film that the inventive method makes has the good optical performance.
Claims (3)
1.Li the method for doping growing P type ZnO crystal film, step is as follows:
To put into the reaction chamber of direct current reaction magnetron sputtering device after the substrate cleaning, reaction chamber vacuum tightness is evacuated to and is higher than 5 * 10
-3Pa is that 0.1～1% zinc lithium alloy is a target with the lithium molar content, with purity oxygen and pure Ar as sputtering atmosphere, with two kinds of gases respectively by mass flowmeter control input buffering chamber, O
2: Ar=1: 2～2: 1, behind the surge chamber thorough mixing, introduce vacuum reaction chamber, under 3～5Pa pressure, underlayer temperature is 400～600 ℃, carries out sputter growth, the growth ending rear film 2～5min that under Ar atmosphere, anneals, annealing temperature is 450～550 ℃.
2. the method for Li doping growing P type ZnO crystal film according to claim 1 is characterized in that oxygen purity is more than 99.99%, and the purity of Ar is more than 99.99%.
3. the method for Li doping growing P type ZnO crystal film according to claim 1 is characterized in that said substrate is silicon or sapphire or quartz or glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100612742A CN1328418C (en) | 2005-10-26 | 2005-10-26 | Process for Li doping growing P type ZnO Single Crystal film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100612742A CN1328418C (en) | 2005-10-26 | 2005-10-26 | Process for Li doping growing P type ZnO Single Crystal film |
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| Publication Number | Publication Date |
|---|---|
| CN1772975A true CN1772975A (en) | 2006-05-17 |
| CN1328418C CN1328418C (en) | 2007-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100612742A Expired - Fee Related CN1328418C (en) | 2005-10-26 | 2005-10-26 | Process for Li doping growing P type ZnO Single Crystal film |
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| CN (1) | CN1328418C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148781B (en) * | 2007-07-27 | 2010-07-28 | 北京大学 | Process for preparing zinc oxide ferro-electricity film |
| CN101671842B (en) * | 2009-10-26 | 2011-07-20 | 浙江大学 | Method for growing Na-N co-doping p-type ZnO crystal film by annealing |
| CN102496578A (en) * | 2011-12-07 | 2012-06-13 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing p-type zinc oxide (ZnO) based thin film in lithium-nitrogen (Li-N) double-acceptor co-doping mode |
| CN104078531A (en) * | 2014-06-30 | 2014-10-01 | 景德镇陶瓷学院 | Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface |
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453840A (en) * | 2003-05-16 | 2003-11-05 | 山东大学 | Prepn of P-type zinc oxide film |
| CN1265434C (en) * | 2003-11-04 | 2006-07-19 | 浙江大学 | Method for preparing p type crystal film |
-
2005
- 2005-10-26 CN CNB2005100612742A patent/CN1328418C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148781B (en) * | 2007-07-27 | 2010-07-28 | 北京大学 | Process for preparing zinc oxide ferro-electricity film |
| CN101671842B (en) * | 2009-10-26 | 2011-07-20 | 浙江大学 | Method for growing Na-N co-doping p-type ZnO crystal film by annealing |
| CN102496578A (en) * | 2011-12-07 | 2012-06-13 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing p-type zinc oxide (ZnO) based thin film in lithium-nitrogen (Li-N) double-acceptor co-doping mode |
| CN104078531A (en) * | 2014-06-30 | 2014-10-01 | 景德镇陶瓷学院 | Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface |
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1328418C (en) | 2007-07-25 |
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