CN102392215A - Preparation method of polycrystalline zinc nitride film - Google Patents
Preparation method of polycrystalline zinc nitride film Download PDFInfo
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- CN102392215A CN102392215A CN2011103692496A CN201110369249A CN102392215A CN 102392215 A CN102392215 A CN 102392215A CN 2011103692496 A CN2011103692496 A CN 2011103692496A CN 201110369249 A CN201110369249 A CN 201110369249A CN 102392215 A CN102392215 A CN 102392215A
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Abstract
The invention discloses a preparation method of a polycrystalline zinc nitride film, belonging to the technical field of electronic materials, characterized in that: a polycrystalline Zn3N2 film is prepared at room temperature by reactive radio-frequency magnetron sputtering on a quartz substrate, the sputtering target is a pure metal Zn target, the distance between the sputtering target and the substrate is 50-80 mm, the basic vacuum of a sputtering chamber is less than 1.0*10<-3> Pa, the sputtering gas is argon, the reactive gas is ammonia, the flow range of the ammonia is 1-5 sccm, the flow range of the argon is 15-19 sccm, and the total flow of the argon and the ammonia is 20 sccm; the pressure intensity of the argon-ammonia mixed gas in the sputtering chamber is 0.5-2.5 Pa, the radio-frequency sputtering power is 30-200 w, and the temperature of the substrate is room temperature. The invention has the advantages of low cost, convenient preparation of target material, recycle target material, and no need of heating the substrate, and the prepared polycrystalline zinc nitride film has large optical band gap.
Description
(1) technical field:
The present invention relates to a kind of preparation method of polycrystalline zinc nitride film, belong to technical field of electronic materials.
(2) background technology:
Semiconductor material is the important component part of modern materials science, plays a part very important to the development of modern civilization.The multiple binary compound material of zinc particularly ZnO material has obtained extensive studies; The adulterated ZnO of P type is the basis of preparation ZnO junction device; Be the key that realizes the zno-based photoelectric device, to solve novel Zn O short-wave long light-emitting device, to widen aspect such as ZnO film Application Areas significant.Zn
3N
2Be considered to prepare the important potential material of adulterated ZnO material of high quality P type and photodiode, have great commercial value, yet its research is also less relatively.Use Zn
3N
2Film is as presoma, through thermooxidizing Zn
3N
2Film preparation P type ZnO film, this method can provide enough active N doped source, improve the solid solubility of N in ZnO.Through to Zn
3N
2Zn is found in the research of method for manufacturing thin film
3N
2Film is very important but research is less relatively, to Zn
3N
2The electricity of film and the research of optical property are fewer, even about Zn
3N
2All there is dispute widely in the energy gap of film self.The difference of preparation method and growth conditions is very remarkable to the influence of its band gap.
Retrieval through to existing document is found, preparation Zn
3N
2The method of the film rf magnetron sputtering Zn that responds
3N
2Ceramic target prepares Zn in quartz substrate
3N
2Film, " using and reacting rf magnetron sputtering Zn referring to people such as Shandong University ancestor Fujian
3N
2Ceramic target prepares Zn in quartz substrate
3N
2The optical band gap of film "; " applied surface science " 252 (2006) 7983-7986 (Fujian Zong; Honglei Ma; Wei Du, et al.Optical band gap of zinc nitride films prepared on quartz substrates from a zinc nitride target by reactive rf magnetron sputtering, Applied Surface Science 252 (2006) 7983-7986); Reaction rf magnetron sputtering Metal Zn target prepares Zn in quartz substrate
3N
2Film, referring to people such as the Zhang Jun of Lanzhou University " underlayer temperature and nitrogen partial pressure are to Zn
3N
2The performance impact of film "; " semi-conductor journal " 28 (2007) 1173-1178 (zhang Jun; Xie Erqing; Fu Yujun, et al.Influence of substrate temperature and nitrogen gas on zinc nitride thin films prepared by rf reactive sputtering, Chinese Journal of Semiconductors 28 (2007) 1173-1178).
With reaction rf magnetron sputtering Zn
3N
2Ceramic target prepares Zn in quartz substrate
3N
2Film, sputter gas adopts 99.999% high-purity N
2, N
2Air pressure maintains 1.2Pa by force, sputtering power 110W, underlayer temperature room temperature.Polycrystalline Zn
3N
2Film presents (321) and (442) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.12eV.Zn
3N
2The ceramic target complicated process of preparation, the cost of target is high, and target can not be recycled, and does not have the target manufacturer production in the market and sells Zn
3N
2Ceramic target.Prepare Zn with reaction rf magnetron sputtering Metal Zn target in quartz substrate
3N
2Film, sputter gas adopts N
2-Ar mixed gas, sputter gas pressure maintains 1.2Pa, sputtering power 50W, 200 ℃ of underlayer temperatures.Polycrystalline Zn
3N
2Film presents (321) preferred orientation, belongs to direct band-gap semicondictor, N
2The optical band gap of sample is 1.23eV during dividing potential drop 50%.The Metal Zn target is than Zn
3N
2Ceramic target is easily manufactured, but the substrate heating makes complex process, and the optical band gap of film is less.
(3) summary of the invention:
The objective of the invention is to overcome the deficiency in the above-mentioned prior art and a kind of method that on quartz substrate, prepares polycrystalline zinc nitride film with reaction rf magnetron sputtering Metal Zn target is provided; This method is with low cost, target is easily manufactured and recyclable utilization, substrate do not need heating, made Zn
3N
2The Film Optics band gap is big.
The object of the invention can reach through following measure:
A kind of preparation method of polycrystalline zinc nitride film is characterized in that sputter gas adopts Ar gas, and reactant gases adopts NH
3Gas, room temperature preparation goes out polycrystalline Zn on quartz substrate
3N
2Film, step is following:
(1) highly purified Metal Zn target is installed in the negative electrode target groove of water-cooled of sputtering chamber of rf magnetron sputtering device; The quartz substrate of cleaning is put into substrate holder; Insert substrate holder in the substrate rotating disk of sputtering chamber, the distance between adjustment Zn target and the substrate is 50-80mm;
(2) sputtering chamber is bled, the base vacuum that makes sputtering chamber is less than 1.0 * 10
-3Pa, the underlayer temperature room temperature;
(3) in sputtering chamber, charge into sputter gas Ar and reactant gases NH
3, the flow of Ar gas and NH
3The flow of gas is independently controlled with mass flowmeter respectively, NH
3The flow range of gas is at 1-5sccm, and the flow range of Ar gas is at 15-19sccm, Ar gas and NH
3The flow summation 20sccm of gas;
(4) adjusting control valve reduces rate of air sucked in required, makes the Ar-NH of sputtering chamber
3The gas pressure intensity of mixed gas is 0.5-2.5Pa, radio-frequency sputtering power 30-200W, and last rf magnetron sputtering makes polycrystalline Zn
3N
2Film.
The purity of Metal Zn target is greater than 99.99wt.% in the above-mentioned steps (1).
In the above-mentioned steps (1) the Metal Zn target be shaped as circle, diameter is 60mm.
The purity of sputter gas Ar gas is 99.99% in the above-mentioned steps (3), reactant gases NH
3The purity of gas is 99.9%.
Under preferred processing condition, promptly the distance between Zn target and the substrate is 60mm, the base vacuum 6.0 * 10 of sputtering chamber
-4Pa, the flow 16sccm of sputter gas Ar gas, reactant gases NH
3The flow 4sccm of gas, the Ar-NH of sputtering chamber
3The gas pressure intensity of mixed gas is 1.0Pa, and radio-frequency sputtering power 70W makes polycrystalline zinc nitride film and presents (321) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.63eV.
Method of the present invention compared with prior art excellent results is following:
With reaction rf magnetron sputtering Zn
3N
2Ceramic target prepares polycrystalline Zn in quartz substrate
3N
2Film, Zn
3N
2The ceramic target complicated process of preparation, the cost of target is high, and target can not be recycled, and does not have the target manufacturer production in the market and sells Zn
3N
2Ceramic target.Prepare polycrystalline Zn with reaction rf magnetron sputtering Metal Zn target in quartz substrate
3N
2Film, the substrate heating makes complex process, and the optical band gap of film is less, and 1.23eV is only arranged.Method of the present invention prepares polycrystalline Zn
3N
2Film, this method is with low cost, target is easily manufactured and recyclable utilization, substrate do not need heating, made Zn
3N
2The Film Optics band gap is big.
(4) embodiment: following specific embodiments of the invention elaborates:
Embodiment 1:
(1) with purity 99.99wt.9%; The Metal Zn target of diameter 60mm is installed in the negative electrode target groove of water-cooled of sputtering chamber of rf magnetron sputtering device; The quartz substrate of cleaning is put into substrate holder; Insert substrate holder in the substrate rotating disk of sputtering chamber, the distance between adjustment Zn target and the substrate is 60mm;
(2) sputtering chamber is bled, the base vacuum that makes sputtering chamber is 6.0 * 10
-4Pa, the underlayer temperature room temperature.
(3) in sputtering chamber, charging into purity is that 99.99% sputter gas Ar and purity are 99.9% reactant gases NH
3, NH
3The flow 4sccm of gas, the flow 16sccm of Ar gas, Ar gas and NH
3The flow summation 20sccm of gas.
(4) adjusting control valve reduces rate of air sucked in required, makes the Ar-NH of sputtering chamber
3The gas pressure intensity of mixed gas is 1.0Pa, radio-frequency sputtering power 70W, film thickness 400nm.Make polycrystalline zinc nitride film and present (321) preferred orientation, belong to indirect band-gap semiconductor, band gap width 2.63eV.
Embodiment 2:
Sputtering target is identical with embodiment 1, and the distance in the step (1) that different is between Zn target and the substrate is 50mm, sputtering chamber base vacuum 9.0 * 10 in the step (2)
-4Pa, NH in the step (3)
3The flow 1sccm of gas, the flow 19sccm of Ar gas, the Ar-NH of sputtering chamber in the step (4)
3The gas pressure intensity of mixed gas is 0.5Pa, radio-frequency sputtering power 30W.Other preparation condition of film is identical with embodiment 1.Make polycrystalline Zn
3N
2Film presents (321) and (222) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.33eV.
Embodiment 3:
Sputtering target is identical with embodiment 1, step (1) that different is hit and substrate between distance be 80mm, NH in the step (3)
3The flow 2sccm of gas, the flow 18sccm of Ar gas, the Ar-NH of sputtering chamber in the step (4)
3The gas pawl of mixed gas is by force 2.5Pa, radio-frequency sputtering power 200W.Other preparation condition of film is identical with embodiment 1.Make polycrystalline Zn
3N
2Film presents (321) and (222) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.38eV.
Embodiment 4:
Sputtering target is identical with embodiment 1, step (1) that different is hit and substrate between distance be 70mm, NH in the step (3)
3The flow 3sccm of gas, the flow 17sccm of Ar gas, the Ar-NH of sputtering chamber in the step (4)
3The gas pressure intensity of mixed gas is 2.0Pa, radio-frequency sputtering power 150W.Other preparation condition of film is identical with embodiment 1.Make polycrystalline Zn
3N
2Film presents (321) and (222) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.58eV.
Embodiment 5:
Sputtering target is identical with embodiment 1, and that different is NH in the step (3)
3The flow 5sccm of gas, the flow 15sccm of Ar gas, the Ar-NH of sputtering chamber in the step (4)
3The gas pressure intensity of mixed gas is 1.5Pa, radio-frequency sputtering power 50W.Other preparation condition of film is identical with embodiment 1.Make polycrystalline Zn
3N
2Film presents (321) preferred orientation, belongs to indirect band-gap semiconductor, band gap width 2.70eV.
Claims (4)
1. the preparation method of a polycrystalline zinc nitride film, step is following:
(1) highly purified Metal Zn target is installed in the negative electrode target groove of water-cooled of sputtering chamber of rf magnetron sputtering device; The quartz substrate of cleaning is put into substrate holder; Insert substrate holder in the substrate rotating disk of sputtering chamber, the distance between adjustment Zn target and the substrate is 50-80mm;
(2) sputtering chamber is bled, the base vacuum that makes sputtering chamber is less than 1.0 * 10
-3Pa, the underlayer temperature room temperature;
(3) in sputtering chamber, charge into sputter gas Ar and reactant gases NH
3, the flow of Ar gas and NH
3The flow of gas is independently controlled with mass flowmeter respectively, NH
3The flow range of gas is at 1-5sccm, and the flow range of Ar gas is at 15-19sccm, Ar gas and NH
3The flow summation 20sccm of gas;
(4) adjusting control valve reduces rate of air sucked in required, makes the Ar-NH of sputtering chamber
3The gas pressure intensity of mixed gas is 0.5-2.5Pa, radio-frequency sputtering power 30-200W, and last rf magnetron sputtering makes polycrystalline Zn
3N
2Film.
2. the preparation method of a kind of polycrystalline zinc nitride film according to claim 1, the purity that it is characterized in that Metal Zn target in the said step (1) is greater than 99.99wt.%.
3. the preparation method of a kind of polycrystalline zinc nitride film according to claim 1 is characterized in that the circle that is shaped as of Metal Zn target in the said step (1), and diameter is 60mm.
4. the preparation method of a kind of polycrystalline zinc nitride film according to claim 1 is characterized in that the purity of sputter gas Ar gas in the said step (3) is 99.99%, reactant gases NH
3The purity of gas is 99.9%.
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|---|---|---|---|
| CN2011103692496A CN102392215A (en) | 2011-11-11 | 2011-11-11 | Preparation method of polycrystalline zinc nitride film |
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|---|---|---|---|
| CN2011103692496A CN102392215A (en) | 2011-11-11 | 2011-11-11 | Preparation method of polycrystalline zinc nitride film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914078A (en) * | 2018-08-07 | 2018-11-30 | 泉州市康馨化工科技有限公司 | The preparation method of the zinc nitride system laminated film of performance improvement |
| CN112794294A (en) * | 2021-01-05 | 2021-05-14 | 段文轩 | Preparation of high-purity zinc nitride powder material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463469A (en) * | 2007-12-21 | 2009-06-24 | 闫金承 | Method for preparing zinc nitride film |
-
2011
- 2011-11-11 CN CN2011103692496A patent/CN102392215A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463469A (en) * | 2007-12-21 | 2009-06-24 | 闫金承 | Method for preparing zinc nitride film |
Non-Patent Citations (2)
| Title |
|---|
| MASANOBU FUTSUHARA, ET AL.: "Structural, electrical and optical properties of zinc nitride thin films prepared by reactive rf magnetron sputtering", 《THIN SOLID FILMS》 * |
| ZHANG JUN，ET AL.: "Influence of Substrate Temperature and Nitrogen Gas on Zinc Nitride Thin Films Prepared by RF Reative Sputtering", 《半导体学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914078A (en) * | 2018-08-07 | 2018-11-30 | 泉州市康馨化工科技有限公司 | The preparation method of the zinc nitride system laminated film of performance improvement |
| CN112794294A (en) * | 2021-01-05 | 2021-05-14 | 段文轩 | Preparation of high-purity zinc nitride powder material |
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Application publication date: 20120328 |