CN102268638A - In and Nb codoped ZnO-based transparent conductive film and preparation method thereof - Google Patents
In and Nb codoped ZnO-based transparent conductive film and preparation method thereof Download PDFInfo
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- CN102268638A CN102268638A CN2011101886054A CN201110188605A CN102268638A CN 102268638 A CN102268638 A CN 102268638A CN 2011101886054 A CN2011101886054 A CN 2011101886054A CN 201110188605 A CN201110188605 A CN 201110188605A CN 102268638 A CN102268638 A CN 102268638A
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Abstract
The invention discloses an In and Nb codoped ZnO-based transparent conductive film and a preparation method thereof, and belongs to the field of functional materials. A target is a ceramic target prepared by mixing high-purity In2O3, Nb2O5 and ZnO powder and performing solid phase sintering. The preparation method comprises the following steps of: putting an In and Nb codoped ZnO ceramic target and cleaned substrates into a growth chamber of a pulse laser deposition device, and preparing In and Nb codoped ZnO-based transparent conductive films with good photoelectric properties on different substrates by regulating deposition process parameters through a pulse laser deposition method. A coating process is simplified, and electron concentration can be controlled by regulating In and Nb content in the target; multiple metal cations are simultaneously doped on the same target; and the prepared In and Nb codoped ZnO-based transparent conductive film has good photoelectric properties, the resistivity of 10<-3>-10<-4>ohm.cm, and the average visible light transmittance of over 87 percent. The transparent conducive film prepared by the method has wide application prospect in the fields of solar batteries and novel photoelectric devices.
Description
Technical field
The invention belongs to field of functional materials, it is ZnO-based transparent conductive film co-doped and preparation method thereof to relate to a kind of In, Nb, is specifically related to a kind of method of utilizing pulsed laser deposition to prepare the n type transparent conducting ZnO film of In, Nb codoped.
Background technology
Transparent conductive film be visible region printing opacity (T〉80 %), ultraviolet region by, and have low resistivity (r＜10
-4Ω cm) a kind of function film.Transparent conductive film mainly is divided into: metallic membrane system, transparent conductive oxide (TCO), polymeric membrane system, compound film system, other compound film systems etc., wherein the TCO film is the widespread use of industry at present.
Tin indium oxide (ITO) transparent conductive film is as a kind of TCO film, based on its high transmission rate (T〉90 %), low-resistivity (r＜10
-4Ω cm) and easily high-performance such as etching is the main product in present TCO film market.Yet indium tin oxide transparent conducting film also has the shortcoming of himself, and as the prices of raw and semifnished materials costliness of ITO target, indium tin mineral resource lacks relatively, shortcoming such as erosion resistance not.
Along with the rise of indium, the tin prices of raw and semifnished materials, people begin to turn to searching can substitute the transparent conductive film material of indium tin oxide films, and are wherein paid attention to most based on the doping film of zinc oxide.Pure ZnO is a kind of broad stopband direct band-gap semicondictor material.The zno-based transparent conductive film is a kind of important photoelectricity information material, and it is abundant that it possesses starting material cheapness and earth reserves, advantage such as stable in the hydrogen plasma ambient.Discover, through the ZnO film after the special doping have can with the good photoelectric properties of ITO analogy.ZnO film after mixing has good electrically conducting transparent performance, is the ito thin film that is expected to substitute present industrial widespread use most.In ZnO, mix the more of unit doping research reports such as Al, Ga.ZnO mixes the Al film, and lattice distortion is big, especially under than higher doping content situation.In addition, in the growth for Thin Film process, Al shows very high reactivity, and is oxidized easily.These shortcomings can produce a lot of adverse influences to the photoelectric properties of film.
Summary of the invention
The present invention is directed to the deficiency that existing transparent conductive film exists, a kind of ZnO-based transparent conductive film co-doped method of In, Nb that adopts single target to prepare to have good photoelectric characteristic is proposed, by simplifying coating process, make the electroconductibility of film and visible light transmittance rate improve.
First purpose of the present invention, a kind of In, Nb are ZnO-based transparent conductive film co-doped, it is characterized in that, utilize pulsed laser deposition equipment, the ZnO ceramic target of In, Nb codoped is deposited on substrate, make In, Nb is ZnO-based transparent conductive film co-doped, the ZnO-based transparent conductive film co-doped resistivity of described In, Nb is minimum to be 8.5 * 10
-4Ω cm, at the visible region average transmittance greater than 87%.
Second purpose of the present invention, the preparation method that a kind of In, Nb are ZnO-based transparent conductive film co-doped is characterized in that, may further comprise the steps:
(1) preparation In, Nb codope ZnO target: with In
2O
3, Nb
2O
5Behind the ZnO powder uniform mixing, compression moulding then at 1000 ℃ ~ 1400 ℃ sintering temperatures, makes In, Nb codope ZnO ceramic target;
(2) preparation In, Nb is ZnO-based transparent conductive film co-doped: the growth room that In, Nb codope ZnO ceramic target and quartz plate that cleaned that step (1) is made or glass substrate substrate are put into the pulsed laser deposition device, distance between target and the substrate is 3cm ~ 6cm, and growth room's vacuum tightness is extracted into pressure less than 8 * 10
-4Pa,, underlayer temperature is 200 ℃ ~ 600 ℃, feed purity in the growth room and be 99.99% oxygen, and oxygen partial pressure is 5pa ~ 10pa, opens laser apparatus, laser frequency 5Hz allows laser beam focus on target material surface ablation target, forms the plumage brightness, deposit on the substrate, depositing time is 40min, under vacuum, and 400 ℃ of annealing 1h, cool to room temperature again makes In, Nb is ZnO-based transparent conductive film co-doped.
In in the described ceramic target of step (1)
2O
3Content be 0.5wt% ~ 2.0wt%, Nb
2O
5Content be 1.0wt% ~ 4.0wt%, surplus is ZnO.
The described substrate of step (2) cleans with ultrasonic wave and acetone successively.
The present invention has following beneficial effect: the first, and the inventive method is simple, by direct doping In in the ZnO powder
2O
3And Nb
2O
5The preparation target has been realized mixing when the multi-element metal positively charged ion is on same target, has simplified coating process; The second, the present invention can be by changing In
2O
3And Nb
2O
5Different ratios adjust the electrology characteristic and the optical characteristics of film; The 3rd, transparent conductive film resistivity when room temperature of the present invention's preparation is minimum to reach 8.5 * 10
-4Ω cm, greater than 87%, the four, the stability of film is better at the visible region average transmittance, and after long-time the placement, the photoelectric properties of film do not have considerable change; The 5th, to mix the Al film with ZnO and compare, it is much smaller that the lattice distortion ratio that mixes the caused ZnO of In among the ZnO is mixed Al, especially under than higher doping content situation; The 6th, mix the Al film with ZnO and compare, in the growth for Thin Film process, Al shows very high reactivity, and is oxidized easily, and In is difficult for oxidized with respect to Al; The 7th, the doping of In and Nb does not change the crystalline structure of ZnO, and prepared film has good (002) preferred orientation: suitably mix Nb in ZnO, the position with Nb replaces Zn forms polyelectrons alms giver Nb
Zn 3+, can regulate the electric property of ZnO effectively; And Nb
+ 5With Zn
+ 2Ionic radius very approaching, when Nb content was not too high, not mixing of Nb can cause big lattice distortion, also can not change the crystalline structure of ZnO.
Description of drawings
Fig. 1 is the ZnO-based transparent conductive film co-doped XRD figure of In, Nb that makes in the example 1 of the present invention;
Fig. 2 is the ZnO-based transparent conductive film co-doped XRD figure of In, Nb that makes in the example 3 of the present invention;
Fig. 3 is the ZnO-based transparent conductive film co-doped XRD figure of In, Nb that makes in the example 4 of the present invention;
Fig. 4 is the change curve of the ZnO-based transparent conductive film co-doped resistivity of the In, the Nb that make in the example 1,3,4,5 of the present invention with underlayer temperature;
Fig. 5 is the change curve of the ZnO-based transparent conductive film co-doped transmittance of the In, the Nb that make in the example 1,3,4,5 of the present invention with underlayer temperature.
Embodiment
The preparation method that a kind of In, Nb are ZnO-based transparent conductive film co-doped:
(1) preparation In, Nb codope ZnO target, the target size is diameter 30mm, thickness 3mm, target is by 1.0wt%In
2O
3+ 2.0wt% Nb
2O
5, compression moulding even with the ZnO powder ground and mixed form at 1200 ℃ of sintering temperatures then.Actual weighing: In
2O
3Be 0.2577g, Nb
2O
5Be 0.5155g, ZnO is 25g.
(2) In that step 1 is prepared, Nb codope ZnO target, with involve the growth room that quartz plate substrate that acetone cleaned is put into the pulsed laser deposition device with ultrasonic, distance between target and the quartz plate substrate is 4cm, and it is 8 * 10 that growth room's vacuum tightness is extracted into pressure
-4Pa, underlayer temperature is 400 ℃, feeding purity is 99.99% oxygen in the growth room, and oxygen partial pressure is 6pa, opens laser apparatus, laser frequency 5Hz, allow laser beam focus on target material surface ablation target, form the plumage brightness, deposit on the substrate, depositing time is 40min, make In, Nb is ZnO-based transparent conductive film co-doped, with the film for preparing under vacuum, 400 ℃ of annealing 1h, cool to room temperature again.
In, the Nb of present embodiment preparation are ZnO-based transparent conductive film co-doped, and resistivity is 1.4 * 10
-3Ω cm, the visible region average transmittance is higher than 85%.Prepared film XRD figure picture as shown in Figure 1, as seen from the figure, film has tangible ZnO(002) peak, the direction of growth along the C axle perpendicular to substrate.After placing the several months, the photoelectric properties of film do not have considerable change.
The preparation method is with embodiment 1, and difference is to be grown on the glass substrate.The ZnO-based transparent conductive film co-doped resistivity of In, Nb of present embodiment preparation is 9.2 * 10
-4Ω cm, the visible region average transmittance is higher than 87%.After placing the several months, the photoelectric properties of film do not have considerable change.
The preparation method that a kind of In, Nb are ZnO-based transparent conductive film co-doped:
(1) preparation In, Nb codope ZnO target, the target size is diameter 30mm, thickness 3mm, target is by 1.5wt%In
2O
3+ 2.0wt% Nb
2O
5, compression moulding even with the ZnO powder ground and mixed form at 1250 ℃ of sintering temperatures then.Actual weighing: In
2O
3Be 0.3886g, Nb
2O
5Be 0.5155g, ZnO is 25g.
(2) In that step 1 is prepared, Nb codope ZnO target, with involve the growth room that quartz plate substrate that acetone cleaned is put into the pulsed laser deposition device with ultrasonic, distance between target and the quartz plate substrate is 4.5cm, and it is 8 * 10 that growth room's vacuum tightness is extracted into pressure
-4Pa, underlayer temperature is 300 ℃, feeding purity is 99.99% oxygen in the growth room, and oxygen partial pressure is 6pa, opens laser apparatus, laser frequency 5Hz, allow laser beam focus on target material surface ablation target, form the plumage brightness, deposit on the substrate, depositing time is 40min, make In, Nb is ZnO-based transparent conductive film co-doped, with the film for preparing under vacuum, 400 ℃ of annealing 1h, cool to room temperature again.
In, the Nb of present embodiment preparation are ZnO-based transparent conductive film co-doped, and resistivity is 7.2 * 10
-3Ω cm, the visible region average transmittance is higher than 87%.Prepared film XRD figure picture as shown in Figure 2, as seen from the figure, film has tangible ZnO(002) peak, the direction of growth along the C axle perpendicular to substrate.After placing the several months, the photoelectric properties of film do not have considerable change.
Embodiment 4
The preparation method that a kind of In, Nb are ZnO-based transparent conductive film co-doped:
(1) preparation In, Nb codope ZnO target, the target size is diameter 30mm, thickness 3mm, target is by 1.5wt%In
2O
3+ 2.0wt% Nb
2O
5, compression moulding even with the ZnO powder ground and mixed form at 1300 ℃ of sintering temperatures then.Actual weighing: In
2O
3Be 0.3886g, Nb
2O
5Be 0.5155g, ZnO is 25g.
(2) In that step 1 is prepared, Nb codope ZnO target, with involve the growth room that quartz plate substrate that acetone cleaned is put into the pulsed laser deposition device with ultrasonic, distance between target and the quartz plate substrate is 4.5cm, and it is 8 * 10 that growth room's vacuum tightness is extracted into pressure
-4Pa, underlayer temperature is 500 ℃, feeding purity is 99.99% oxygen in the growth room, and oxygen partial pressure is 10pa, opens laser apparatus, laser frequency 5Hz, allow laser beam focus on target material surface ablation target, form the plumage brightness, deposit on the substrate, depositing time is 40min, make In, Nb is ZnO-based transparent conductive film co-doped, with the film for preparing under vacuum, 400 ℃ of annealing 1h, cool to room temperature again.
In, the Nb of present embodiment preparation are ZnO-based transparent conductive film co-doped, and resistivity is 8.5 * 10
-4Ω cm, the visible region average transmittance is higher than 85%.Prepared film XRD figure picture as shown in Figure 3, as seen from the figure, film has tangible ZnO(002) peak, the direction of growth along the C axle perpendicular to substrate.After placing the several months, the photoelectric properties of film do not have considerable change.
Embodiment 5
The preparation method that a kind of In, Nb are ZnO-based transparent conductive film co-doped:
(1) preparation In, Nb codope ZnO target, the target size is diameter 30mm, thickness 3mm, target is by 2.0wt%In
2O
3+ 3.0wt% Nb
2O
5, compression moulding even with the ZnO powder ground and mixed form at 1300 ℃ of sintering temperatures then.Actual weighing: In
2O
3Be 0.5263g, Nb
2O
5Be 0.7895g, ZnO is 25g.
(2) In that step 1 is prepared, Nb codope ZnO target, with involve the growth room that quartz plate substrate that acetone cleaned is put into the pulsed laser deposition device with ultrasonic, distance between target and the quartz plate substrate is 5.0cm, and it is 8 * 10 that growth room's vacuum tightness is extracted into pressure
-4Pa, underlayer temperature is 600 ℃, feeding purity is 99.99% oxygen in the growth room, and oxygen partial pressure is 10pa, opens laser apparatus, laser frequency 5Hz, allow laser beam focus on target material surface ablation target, form the plumage brightness, deposit on the substrate, depositing time is 40min, make In, Nb is ZnO-based transparent conductive film co-doped, with the film for preparing under vacuum, 400 ℃ of annealing 1h, cool to room temperature again.
In, the Nb of present embodiment preparation are ZnO-based transparent conductive film co-doped, and resistivity is 9.2 * 10
-4Ω cm, the visible region average transmittance is higher than 88%.After placing the several months, the photoelectric properties of film do not have considerable change.
Claims (4)
1. an In, Nb are ZnO-based transparent conductive film co-doped, it is characterized in that, utilize pulsed laser deposition equipment, the ZnO ceramic target of In, Nb codoped is deposited on substrate, make In, Nb is ZnO-based transparent conductive film co-doped, the ZnO-based transparent conductive film co-doped resistivity of described In, Nb is minimum to be 8.5 * 10
-4Ω cm, the visible region average transmittance is greater than 87%.
2. In as claimed in claim 1, the ZnO-based transparent conductive film co-doped preparation method of Nb is characterized in that, may further comprise the steps:
(1) preparation In, Nb codope ZnO target: with In
2O
3, Nb
2O
5Behind the ZnO powder uniform mixing, compression moulding then at 1000 ℃ ~ 1400 ℃ sintering temperatures, makes In, Nb codope ZnO ceramic target;
(2) In that step (1) is made, Nb codope ZnO ceramic target and the quartz plate that cleaned or glass substrate substrate are put into the growth room of pulsed laser deposition device, distance between target and the substrate is 3cm-6cm, and growth room's vacuum tightness is extracted into pressure less than 8 * 10
-4Pa, underlayer temperature are 200 ℃-600 ℃, and feeding purity is 99.99% oxygen in the growth room, and oxygen partial pressure is 5pa-10pa; Open laser apparatus, laser frequency 5Hz allows laser beam focus on target material surface ablation target, forms the plumage brightness, deposit on the substrate, depositing time is 40min, under vacuum, 400 ℃ of annealing 1h, cool to room temperature again makes In, Nb is ZnO-based transparent conductive film co-doped.
3. In as claimed in claim 2, the ZnO-based transparent conductive film co-doped preparation method of Nb is characterized in that, In in the described ceramic target of step (1)
2O
3Content be 0.5wt% ~ 2.0wt%, Nb
2O
5Content be 1.0wt% ~ 4.0wt%, surplus is ZnO.
4. In as claimed in claim 2, the ZnO-based transparent conductive film co-doped preparation method of Nb is characterized in that, described quartz plate of step (2) or glass substrate substrate clean with ultrasonic wave, acetone successively.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756840A (en) * | 2016-11-28 | 2017-05-31 | 深圳大学 | A kind of high-temperature flexible transparent conductive film and preparation method and application |
| CN108570643A (en) * | 2018-05-18 | 2018-09-25 | 华南师范大学 | A kind of preparation method of Er doping ZnO transparent conductive thin film |
| WO2022156540A1 (en) * | 2021-01-19 | 2022-07-28 | The University Of Hong Kong | Transparent and high-k thin film prepared by pulsed laser deposition |
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| CN101660120A (en) * | 2009-09-15 | 2010-03-03 | 中国科学院上海硅酸盐研究所 | Multi-element doping n-type zinc-oxide-base transparent conducting film and preparation method thereof |
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2011
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| CN101483219A (en) * | 2009-01-15 | 2009-07-15 | 浙江大学 | Co-Ga co-blended ZnO based diluted semi-conductor thin-film and manufacturing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756840A (en) * | 2016-11-28 | 2017-05-31 | 深圳大学 | A kind of high-temperature flexible transparent conductive film and preparation method and application |
| CN108570643A (en) * | 2018-05-18 | 2018-09-25 | 华南师范大学 | A kind of preparation method of Er doping ZnO transparent conductive thin film |
| WO2022156540A1 (en) * | 2021-01-19 | 2022-07-28 | The University Of Hong Kong | Transparent and high-k thin film prepared by pulsed laser deposition |
| CN114807852A (en) * | 2021-01-19 | 2022-07-29 | 香港大学 | Transparent and high-k thin films prepared by pulsed laser deposition |
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Application publication date: 20111207 |