CN103060757B - Method for growing p-type transparent and conducting Ni1-xMgxO crystal film by doping Li - Google Patents
Method for growing p-type transparent and conducting Ni1-xMgxO crystal film by doping Li Download PDFInfo
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- CN103060757B CN103060757B CN201210541828.9A CN201210541828A CN103060757B CN 103060757 B CN103060757 B CN 103060757B CN 201210541828 A CN201210541828 A CN 201210541828A CN 103060757 B CN103060757 B CN 103060757B
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Abstract
The invention relates to a method for growing p-type transparent and conducting Ni1-xMgxO crystal film by doping Li, comprising the following steps: adopting pulse laser deposition method for compression and high-temperature sintering after ball milling and mixing NiO, MgO and Li2CO3 powders so as to manufacture Li-doped Ni1-xMgxO ceramic target; placing the ceramic target and a substrate in a pulse laser deposition device; adjusting the distance between the target and the substrate; growing at proper substrate temperature under proper oxygen pressure intensity and laser frequency; and then cooling till room temperature so as to obtain the Li-doped Ni1-xMgxO crystal film. The crystal film prepared by the method is p-type conducting, and has the excellent characteristics of being low in electrical resistivity, high in transmissivity, high in carrier mobility, continuously adjustable in band gap, and the like; and the method is simple, real-time doping is realized, the doping concentration is controlled by adjusting the growth temperature and the contents of Li and Mg in the target, and the obtained film has wide application prospect in the fields of transparent electronic devices, photoelectronic devices and the like.
Description
Technical field
The present invention relates to a kind of Li doped growing p type electrically conducting transparent Ni
1-xmg
xthe method of O crystal film, belongs to p-type transparent conductive film technical field.
Background technology
Transparent conductive oxide (TCO) film is a kind of important photoelectric material, has a wide range of applications in fields such as solar cell, plate of flat liquid crystal display, photodiodes because the transparency of its uniqueness and electroconductibility are incorporated into one.N-shaped TCO material, as ITO (In
2o
3: Sn), FTO (SnO
2: F) and AZO (ZnO:Al), its photoelectric properties have reached better level, and have been widely used in commercially produced product.
But the kind of corresponding p-type TCO material is few, and its photoelectric properties compare with N-shaped TCO and differ greatly, and thus limit its application in transparent electron and opto-electronic device to a certain extent.Therefore, to explore and research has the p-type TCO thin film material of good photoelectric properties, there is practical significance and the using value widely of reality.
NiO is a kind of intrinsically p-type broad stopband (3.7 eV) semiconductor material typically with direct band gap, NiO and MgO all has a cube NaCl crystalline structure, and lattice parameter is close, NiO lattice parameter is 0.4177 nm, MgO lattice parameter is 0.4212 nm, so can obtain the Ni of any component in theory
1-xmg
xo (O<x<1) unlimited solid solution alloy firm.The energy gap of MgO is 7.8 eV, by mixing Mg in NiO, can regulate continuously, thus realize its energy band engineering to its energy gap.But, the Ni of preparation usually
1-xmg
xo alloy firm presents high resistant, limits it to a great extent as the application of wide bandgap semiconductor materials in opto-electronic device.Theoretical and experimental study shows that Li is a kind of desirable acceptor doping element of NiO, thus passes through Ni
1-xmg
xo crystal film carries out Li acceptor doping also effectively can increase hole in theory, thus reduces its resistivity, is the continuously adjustable Ni of band gap
1-xmg
xthe application of O film in short-wavelength light electron device lays the foundation.Pulsed laser deposition have deposition parameter easily control, easily keep film consistent with target composition, can realize real-time doping and the advantage such as film crystal quality is good, but the report of the p-type NiMgO crystal film up to the present also not having the sharp Li of preparation in this way to adulterate.
Therefore, Li doped growing p type electrically conducting transparent Ni is developed
1-xmg
xo crystal film, has very important realistic meaning.
Summary of the invention
The object of the invention is to overcome that existing p-type TCO thin film material category is few, photoelectric properties are poor so that be difficult to meet the problem of the requirement of optoelectronic device applications, a kind of Li doped growing p type electrically conducting transparent Ni is provided
1-xmg
xthe method of O crystal film.
Above-mentioned purpose of the present invention, is achieved by the following technical programs.
A kind of Li doped growing p type electrically conducting transparent Ni
1-xmg
xthe method of O crystal film, method described in it adopts pulsed laser deposition, and its method steps is as follows:
1) NiO, MgO and Li of purity>=99.99% is weighed
2cO
3powder, wherein the molar content x of Mg is 0<x<40, the molar content y of Li is 0<y<10%, above-mentioned powder ball milling is mixed rear compression moulding, 800 ° of C presintering more than 1 hour, more than 4 hours are sintered again, the obtained Ni mixing Li at 1100 ~ 1200 ° of C
1-xmg
xo ceramic target;
2) by step 1) obtained ceramic target and put into the growth room of pulsed laser deposition device with the substrate after nitrogen dries up with acetone, ethanol and deionized water successively ultrasonic cleaning, distance between target and substrate is 4 ~ 6 cm, and growth room's back end vacuum tightness is evacuated to 10
-4pa, silicon makes temperature remain 300 ~ 500 ° of C, with pure O
2for growth atmosphere, controlling pressure is 0.1 ~ 20 Pa, and laser frequency is 3 ~ 5 Hz, and growth time is 20 ~ 120 min, is cooled to room temperature after growth, obtains Li doped p type electrically conducting transparent Ni
1-xmg
xo crystal film.
In technique scheme, further additional technical feature is:
It obtains Li doped p type electrically conducting transparent Ni
1-xmg
xo crystal film slowly cools to room temperature after in-situ annealing 30 min under oxygen atmosphere protection.
Li doped p type electrically conducting transparent Ni described in it
1-xmg
xthe thickness of O crystal film is 50 ~ 400 nm.
Substrate described in it is silicon, sapphire, glass or quartz.
Realize a kind of Li doped growing p type electrically conducting transparent Ni provided by the present invention
1-xmg
xthe method of O crystal film, be by regulate mix the molar content of Mg and Li, underlayer temperature and growth atmosphere pressure, prepare the band gap continuously adjustable p-type electrically conducting transparent Ni of different levels of doping
1-xmg
xo crystal film, film thickness determined by depositing time, laser work voltage and repetition rate.Its advantage and positively effect are:
The inventive method can realize real-time doping, at Ni
1-xmg
xrealize band gap in O crystal film process of growth to regulate continuously and adulterate with p-type simultaneously.
The inventive method doping content can be controlled by the molar content obtaining Mg and Li in growth regulation temperature and target.
The method of the invention is simple, prepared p-type thin film crystalline quality is excellent, not only maintain a cube NaCl crystalline structure, produce without phase-splitting, and there is low-resistivity, high-transmission rate, high carrier mobility, also have repeatability and stability preferably, the film obtained is with a wide range of applications in the field such as transparent electron and opto-electronic device.
Accompanying drawing explanation
Fig. 1 is the pulsed laser deposition device schematic diagram that the present invention adopts.In figure: 1: laser apparatus; 2: growth room; 3: target; 4: substrate.
Fig. 2 is the p-type Li doping transparent conduction Ni of the embodiment of the present invention 1
1-xmg
xx-ray diffraction (XRD) collection of illustrative plates of O crystal film.
Fig. 3 is the p-type Li doping transparent conduction Ni of the embodiment of the present invention 1
1-xmg
xthe optical transmission spectrum of O crystal film.
Embodiment
Below the specific embodiment of the present invention is further illustrated
Embodiment 1
1) NiO, MgO and Li that purity is 99.99% is weighed
2cO
3powder, wherein the molar content x of MgO is the molar content y of 20%, Li is 4%, by NiO, MgO and Li
2cO
3mixed powder and appropriate ethanol pour into successively and be equipped with in the ball grinder of agate ball, to be placed on ball mill ball milling 24 hours.The object of ball milling has two: be on the one hand in order to by NiO, MgO and Li
2cO
3powder mixes, to ensure the homogeneity of the target material composition prepared; On the other hand in order to by NiO, MgO and Li
2cO
3powder fining, is beneficial to the shaping and sintering of mixed powder subsequently.
After ball milling terminates, separated by raw material and dry, the powder then obtained carries out grinding and compression moulding.Shaping idiosome is put into sintering oven, and first 800 ° of C pre-burnings 1 hour, then sinter more than 4 hours at 1100 ~ 1200 ° of C, obtain thickness and be about 3 mm, diameter is the Ni mixing Li of 50 mm
0.8mg
0.2o circular target.
2) to mix the Ni of Li
0.8mg
0.2o circular is target, to be fixed in the sample table in pulsed laser deposition device with acetone, ethanol and deionized water ultrasonic cleaning by the quartz substrate after nitrogen dries up successively, the distance of adjustment substrate and target is 5 cm, and substrate and target is separated with baffle plate.In growth room, back end vacuum tightness is evacuated to 10
-4pa, then heated substrate, make underlayer temperature be 400 ° of C, with pure O
2(purity 99.99%) is growth atmosphere, control O
2pressure is 5 Pa, and pulsed laser energy is 300 mJ, and laser frequency is 5 Hz, and baffle plate of outwarding winding after first pre-sputtering target 10 min removal target material surface pollutes starts deposition growing, and the time of growth is 60 min, and film thickness is 200 nm.Film after growth slowly cools to room temperature after in-situ annealing 30 min under oxygen atmosphere protection, obtains the Ni of Li doping
0.8mg
0.2o crystal film.Accompanying drawing 2 is shown in by its x-ray diffraction (XRD) collection of illustrative plates, and optical transmission spectrum is shown in accompanying drawing 3.
Obtained Li Ni doped
0.8mg
0.2o crystal film is p-type conductance, at room temperature has excellent photoelectricity performance: resistivity is 23.48 Ω cm, and mobility is 0.61 cm2V
-1s
-1, hole concentration is 4.35 × 10
17cm
-3, visible ray average transmittances more than 70%, optical band gap about 3.9 eV, and the photoelectricity performance of placing several months rear film does not have considerable change.
Embodiment 2
1) NiO, MgO and Li that purity is 99.99% is weighed
2cO
3powder, wherein the molar content x of MgO is the molar content y of 30%, Li is 8%, by NiO, MgO and Li
2cO
3mixed powder and appropriate ethanol pour into successively and be equipped with in the ball grinder of agate ball, to be placed on ball mill ball milling 24 hours.The object of ball milling has two: be on the one hand in order to by NiO, MgO and Li
2cO
3powder mixes, to ensure the homogeneity of the target material composition prepared; On the other hand in order to by NiO, MgO and Li
2cO
3powder fining, is beneficial to the shaping and sintering of mixed powder subsequently.
After ball milling terminates, separated by raw material and dry, the powder then obtained carries out grinding and compression moulding.Shaping idiosome is put into sintering oven, and first 800 ° of C pre-burnings 1 hour, then sinter more than 4 hours at 1100 ~ 1200 ° of C, obtain thickness and be about 3 mm, diameter is the Ni mixing Li of 50 mm
0.7mg
0.3o circular target.
2) to mix the Ni of Li
0.7mg
0.3o circular is target, to be fixed in the sample table in pulsed laser deposition device with acetone, ethanol and deionized water ultrasonic cleaning by the Sapphire Substrate after nitrogen dries up successively, the distance of adjustment substrate and target is 4 cm, and substrate and target is separated with baffle plate.In growth room, back end vacuum tightness is evacuated to 10
-4pa, then heated substrate, make underlayer temperature be 500 ° of C, with pure O
2(purity 99.99%) is growth atmosphere, control O
2pressure is 20 Pa, and pulsed laser energy is 300 mJ, and laser frequency is 5 Hz, and baffle plate of outwarding winding after first pre-sputtering target 10 min removal target material surface pollutes starts deposition growing, and the time of growth is 15 min, and film thickness is 50 nm.Film after growth slowly cools to room temperature after in-situ annealing 30 min under oxygen atmosphere protection, obtains the Ni of Li doping
0.7mg
0.3o crystal film.
Obtained Li Ni doped
0.7mg
0.3o crystal film is p-type conductance, at room temperature has excellent photoelectricity performance: resistivity is 1268 Ω cm, and mobility is 537 cm2V
-1s
-1, hole concentration is 9.16 × 10
12cm
-3, visible ray average transmittances more than 65%, optical band gap about 4.1 eV, and the photoelectricity performance of placing several months rear film does not have considerable change.
Embodiment 3
1) NiO, MgO and Li that purity is 99.99% is weighed
2cO
3powder, wherein the molar content x of MgO is the molar content y of 10%, Li is 4%, by NiO, MgO and Li
2cO
3mixed powder and appropriate ethanol pour into successively and be equipped with in the ball grinder of agate ball, to be placed on ball mill ball milling 24 hours.The object of ball milling has two: be on the one hand in order to by NiO, MgO and Li
2cO
3powder mixes, to ensure the homogeneity of the target material composition prepared; On the other hand in order to by NiO, MgO and Li
2cO
3powder fining, is beneficial to the shaping and sintering of mixed powder subsequently.
After ball milling terminates, separated by raw material and dry, the powder then obtained carries out grinding and compression moulding.Shaping idiosome is put into sintering oven, and first 800 ° of C pre-burnings 1 hour, then sinter more than 4 hours at 1100 ~ 1200 ° of C, obtain thickness and be about 3 mm, diameter is the Ni mixing Li of 50 mm
0.9mg
0.1o circular target.
2) to mix the Ni of Li
0.9mg
0.1o circular is target, to be fixed in the sample table in pulsed laser deposition device with acetone, ethanol and deionized water ultrasonic cleaning by the glass substrate after nitrogen dries up successively, the distance of adjustment substrate and target is 6 cm, and substrate and target is separated with baffle plate.In growth room, back end vacuum tightness is evacuated to 10
-4pa, then heated substrate, make underlayer temperature be 300 ° of C, with pure O
2(purity 99.99%) is growth atmosphere, control O
2pressure is 0.1 Pa, and pulsed laser energy is 300 mJ, and laser frequency is 5 Hz, and baffle plate of outwarding winding after first pre-sputtering target 10 min removal target material surface pollutes starts deposition growing, and the time of growth is 120 min, and film thickness is 400 nm.Film after growth slowly cools to room temperature after in-situ annealing 30 min under oxygen atmosphere protection, obtains the Ni of Li doping
0.9mg
0.1o crystal film.
Obtained Li Ni doped
0.9mg
0.1o crystal film is p-type conductance, at room temperature has excellent photoelectricity performance: resistivity is 111 Ω cm, and mobility is 30.5 cm2V
-1s
-1, hole concentration is 1.84 × 10
15cm
-3, visible ray average transmittances more than 60%, optical band gap about 3.8 eV, and the photoelectricity performance of placing several months rear film does not have considerable change.
Claims (2)
1. a Li doped growing p type electrically conducting transparent Ni
1-xmg
xthe method of O crystal film, comprises pulsed laser deposition, and its concrete grammar step is as follows:
1) by NiO, MgO and Li of purity>=99.99%
2cO
3powder, wherein the molar content x of Mg is 0<x<40%, the molar content y of Li is 0<y<10%, ball milling mixes rear compression moulding, 800 ° of C presintering more than 1 hour, more than 4 hours are sintered again, the obtained Ni mixing Li at 1100 ~ 1200 ° of C
1-xmg
xo ceramic target;
2) by above-mentioned steps 1) the obtained Ni mixing Li
1-xmg
xo ceramic target with insert in the growth room of pulsed laser deposition device with the substrate that nitrogen dries up with acetone, ethanol and deionized water successively ultrasonic cleaning, the distance adjusted between target and substrate is 4 ~ 6 cm, and growth room's back end vacuum tightness is 10
-4pa, substrate heating temperature is 300 ~ 500 ° of C, is the O of 99.99% with purity
2for growth atmosphere, controlling pressure is 0.1 ~ 20 Pa, and laser frequency is 3 ~ 5 Hz; growth time is 20 ~ 120 min, grows, in-situ annealing 30 min under oxygen atmosphere protection; after be cooled to room temperature, obtaining thickness is the Li doped p type electrically conducting transparent Ni of 50 ~ 400 nm
1-xmg
xo crystal film.
2. method according to claim 1, substrate described in it is silicon, sapphire, glass or quartz.
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| CN108545787B (en) * | 2018-05-10 | 2019-08-20 | 浙江大学 | Hot injection method prepares nickel oxide and mixes the nanocrystalline method with nickel oxide film of lithium |
| CN116332623B (en) * | 2023-03-27 | 2024-06-11 | 深圳众诚达应用材料股份有限公司 | NMO oxide semiconductor material, and preparation method and application thereof |
| CN116768606A (en) * | 2023-06-06 | 2023-09-19 | 先导薄膜材料（广东）有限公司 | Composite nickel magnesium oxide target and preparation method thereof |
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|---|---|---|---|---|
| CN101521247A (en) * | 2007-07-12 | 2009-09-02 | 应用材料公司 | Method for the generation of a transparent conductive oxide coating |
| CN102560361A (en) * | 2012-02-28 | 2012-07-11 | 杭州电子科技大学 | P-type transparent conductive lithium-doped nickel oxide film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101521247A (en) * | 2007-07-12 | 2009-09-02 | 应用材料公司 | Method for the generation of a transparent conductive oxide coating |
| CN102560361A (en) * | 2012-02-28 | 2012-07-11 | 杭州电子科技大学 | P-type transparent conductive lithium-doped nickel oxide film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "磁控溅射法制备MgxNi1-xO薄膜及其表征";张志刚;《中国优秀硕士学位论文全文数据库》;20061231;第7页第1段，第10页第3段，第18页第2-4段，第19页第3-5段，第22页第1段，第25页第2段，第39页第2段，第40页第1段 * |
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