CN107705873A - A kind of transparent conducting glass and its preparation method and application - Google Patents
A kind of transparent conducting glass and its preparation method and application Download PDFInfo
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Abstract
This application discloses a kind of transparent conducting glass and its preparation method and application.The transparent conducting glass of the application, including amorphous substrate and the transparent conductive film that is attached on amorphous substrate, wherein, transparent conductive film is the metal-doped titanium deoxid film of Anatase (004) orientation.The transparent conducting glass of the application, take the lead in foring the metal-doped titanium deoxid film that arrangement consistent Anatase (004) in grain growth direction is orientated on amorphous substrate, substantially increase the electric conductivity of transparent conducting glass.Also, the transparent conducting glass of the application, preparation method is simple, easy to operate, cost is low, produced suitable for large area；Anatase (004) degree of orientation is controllable in metal-doped titanium deoxid film prepared by the preparation method of the application, can meet different use demands.
Description
Technical field
The application is related to transparent conductive film field, more particularly to a kind of transparent conducting glass and preparation method thereof and answers
With.
Background technology
With the fast development of Flexible Displays industry in world wide, the transparent conductive oxide (abbreviation TCO) of large area
The demand of glass substrate will keep rapidly increasing for a long time.According to initial estimate, to the year two thousand twenty world wide in TCO glass substrates
Demand will be more than 1,200,000,000 square metres.The existing wide variety of nesa coating of industrial circle mainly includes tin indium oxide (abbreviation
ITO), zinc oxide aluminum (abbreviation AZO) and fluorine-doped tin oxide (abbreviation FTO) three major types.Wherein ITO uses expensive indium because a large amount of
Material, it is extremely restricted its application.The photoelectric properties of FTO and AZO systems are horizontal close to ITO, in flat-panel monitor
To certain applications, but need to introduce high-temperature technology in FTO and AZO preparation process, higher is required to working condition, therefore
Extensive use to FTO and AZO causes limitation.
In order to further reduce cost, avoid using rare metal indium, and do not reduce the performance of conductive film, TCO is existed
Competitive advantage is had more in production, titanium dioxide base film has attracted people with its excellent photoelectric properties and inexpensive and aboundresources
Extensive concern.But in magnetron sputtering, the titanium dioxide base film of unformed substrate grown often shows (101) and taken
To growth, the carrier mobility of the titanium dioxide conducting film of (101) orientation is very low, significantly limit Thin film conductive performance
Improve.And the film of (004) preferential growth then has higher carrier mobility, be (101) orientation 3-6 times, so as to
Excellently to improve electric conductivity.
In the prior art, grow the method for (004) orientation titanium dioxide based conductive film, only two methods, i.e., beyond
Prolong substrate and carry out epitaxial growth and with Ca2Nb3O10Epitaxial growth is carried out after nanometer sheet modification substrate.Wherein, entered with epitaxial substrate
This method of row epitaxial growth, because preparing limited area and costly, laboratory use can only be limited to.And with Ca2Nb3O10Receive
This method of rice piece modification substrate, then add the complexity of preparation, and Ca2Nb3O10Nanometer sheet often using czochralski method come
Realize, this adds increased substrate to modify difficulty.
The content of the invention
The purpose of the application is to provide a kind of transparent conducting glass of neotectonics and its preparation method and application.
The application employs following technical scheme：
On the one hand the application discloses a kind of transparent conducting glass, including amorphous substrate and be attached on amorphous substrate
Transparent conductive film, wherein, transparent conductive film be Anatase (004) orientation metal-doped titanium deoxid film.
It should be noted that the key of the application is to prepare to form Anatase (004) orientation on amorphous substrate
Metal-doped titanium deoxid film because (004) orientation metal-doped titanium deoxid film have higher carrier move
Shifting rate, so substantially increasing the electric conductivity of transparent conducting glass.Although (004) the metal-doped titanium deoxid film of orientation
Crystal phase structure is known per se, also, it is also known that it, which has high carrier mobility,；But generally in amorphous lining
The metal-doped titanium deoxid film to form (101) orientation can only be prepared on bottom, it is impossible to form metal-doped the two of (004) orientation
Thin film of titanium oxide, the application are prepared in amorphous substrate by special preparation method and form what Anatase (004) was orientated
Metal-doped titanium deoxid film, so as to propose a kind of excellent transparent conducting glass of new electric conductivity.
Preferably, the grain growth direction arrangement of conductive film is consistent.
Preferably, doped chemical is niobium and/or tantalum in metal-doped titanium deoxid film.
Preferably, the amount of the doping of niobium is the 0.1-20% of gross weight, and the amount of tantalum doping is the 0.1-20% of gross weight；It is excellent
Choosing, the amount of the doping of niobium is the 1.5-7% of gross weight, and the amount of tantalum doping is the 1.5-7% of gross weight.
Preferably, amorphous substrate is glass, quartz, polyimides, polyethylene terephthalate and makrolon
At least one of.
The another side of the application discloses application of the transparent conducting glass of the application in combination electrode.
The preparation method of the transparent conducting glass for simultaneously disclosing the application again of the application, including use magnetron sputtering skill
Art, sputtering power 0.5-3.0W/cm2, sputtered with the inclination angle of 1-60 degree in amorphous substrate surface, in amorphous lining
Basal surface forms film, and then carrying out annealing makes thin film crystallization, and the titanium dioxide for obtaining Anatase (004) orientation is thin
Film, that is, form transparent conducting glass；Inclination angle refers to that plasma sputter line deviates the angle of vertical ion line.
Preferably, the angle at inclination angle is 10-60 degree.
Preferably, the angle at inclination angle is 11-30 degree.
It should be noted that the application can form the titanium deoxid film of (004) orientation on amorphous substrate, it is closed
Key is, using inclination angle magnetron sputtering and coordinates specific sputtering power, i.e., is sputtered with certain inclination angle, also,
In certain limit, (004) degree of orientation is bigger in inclined bigger the formed titanium deoxid film of angle.It is appreciated that only
If inclination angle magnetron sputtering, no matter angular dimension, the titanium deoxid film of (004) orientation can be all formed, simply inclination angle is smaller,
Such as in the case of only 1 degree, (004) degree of orientation meeting very little, the raising of its electric conductivity is also with regard to corresponding small；At inclination angle
When reaching 11 degree and the above, (004) degree of orientation can greatly improve, and corresponding electric conductivity also has preferable improvement.
Preferably, the condition of annealing is that in vacuum or inert atmosphere or reducing atmosphere, 250-650 DEG C is incubated 0-
10h；Preferable annealing condition is, in vacuum or inert atmosphere or reducing atmosphere, 350-400 DEG C of insulation 0.5-1h.
It should be noted that the purpose of annealing is to make titanium dioxide crystal, metal-doped the two of (004) orientation is formed
Thin film of titanium oxide, it will be understood that the film layer that surface sputters before annealing is amorphous state, by annealing
Afterwards, film layer crystallizes, so as to form the titania-doped film of transparent metal of conductive energy.
Preferably, the preparation method of the application, chloride solution immersion is carried out before annealing, in addition to film
At processing, film surface deposited metal or semiconductor or high molecular polymer processing, UV ozone radiation treatment, infrared irridiation
At least one of reason.
It should be noted that the purpose of processing is to carry out other modifications to titanium deoxid film above, with further
The electric conductivity and/or light transmittance of film are improved, its concrete technology condition may be referred to existing titanium deoxid film surface treatment
Technique.Such as a kind of transparent conductive film and preparation method thereof was just disclosed in patent application CN106191775A, it is handled
Technique can use for reference the application.
The beneficial effect of the application is：
The transparent conducting glass of the application, the metal for Anatase (004) orientation that takes the lead in foring on amorphous substrate
Titania-doped film, substantially increase the electric conductivity of transparent conducting glass.Also, the transparent conducting glass of the application,
Preparation method is simple, easy to operate, cost is low, is produced suitable for large area；It is metal-doped prepared by the preparation method of the application
Anatase (004) degree of orientation is controllable in titanium deoxid film, can meet different use demands.
Brief description of the drawings
Fig. 1 is the schematic diagram of inclination angle magnetron sputtering in the embodiment of the present application；
Fig. 2 is the XRD of metal-doped titanium deoxid film in the embodiment of the present application；
Fig. 3 is the SEM figures of metal-doped titanium deoxid film in the embodiment of the present application；
Fig. 4 is the XRD of metal-doped titanium deoxid film in another embodiment of the application；
Fig. 5 is the SEM figures of metal-doped titanium deoxid film in another embodiment of the application；
Fig. 6 is the transmission spectrogram of metal-doped titanium deoxid film in another embodiment of the application；
Fig. 7 is the XRD of metal-doped titanium deoxid film in another embodiment of the application；
Fig. 8 is the SEM figures of metal-doped titanium deoxid film in another embodiment of the application；
Fig. 9 is the XRD of metal-doped titanium deoxid film in another embodiment of the application；
Figure 10 is the SEM figures of metal-doped titanium deoxid film in another embodiment of the application.
Embodiment
The metal-doped titanium deoxid film of Anatase (004) orientation has higher carrier mobility, Neng Gouti
Its high electric conductivity, this is well known to those skilled in the art.But the metal-doped titanium dioxide of Anatase (004) orientation
Titanium film can only be carried out epitaxial growth with epitaxial substrate or with Ca2Nb3O10Epitaxial growth is carried out after nanometer sheet modification substrate, no
Directly it can be generated on amorphous substrate；On the one hand, the metal-doped titanium dioxide of existing two kinds of Anatases (004) orientation
Method for manufacturing thin film cost is high, it is complicated to prepare, difficulty height, and is not suitable for large area production；On the other hand, because it can not directly exist
Generated on amorphous substrate, also limit its application in transparent conducting glass.
It is typically only capable to generate the metal-doped titanium deoxid film of anatase (101) orientation, this Shen on amorphous substrate
Inventor please is forming the research process discovery of metal-doped titanium deoxid film, usual ion beam current using magnetron sputtering
All it is to face workpiece or amorphous substrate, vertically beats on surface, form sputtered film；But sent out during experiment
It is existing, if ion beam current and it is non-perpendicular be mapped to amorphous substrate surface, but amorphous substrate surface is mapped to certain inclination angle,
Also, under the conditions of certain sputtering power, the titania-doped film of a certain degree of (004) orientation metal can be formed, is inclined
Oblique angle is bigger, and (004) degree of orientation is bigger.The application by it is this with certain inclination angle be splashed to amorphous substrate surface formed it is thin
The sputtering of film is defined as inclination angle magnetron sputtering.
The inclination angle magnetron sputtering of the application includes three kinds of forms, as shown in figure 1, Fig. 1 shows the inclination angle in the case of three kinds
Magnetron sputtering, in Fig. 1, A is amorphous substrate, B is target, and 1,2,3,4,5,6 be six different positions, (a), (b), (c)
Three figures are respectively inclination angle sputtering of the amorphous substrate in target different azimuth.Wherein, form one, (a) figure institute in Fig. 1
Show, during the vertical substrate of sputter direction, such as target is in position 1, it is believed that inclination angle is 0 °, when target moves in horizontal two-dimension face
When, it is believed that belong to inclination angle sputtering；As shown in (a) figure in Fig. 1, inclination angle of the target at position 5 is θ, and the inclination angle theta is the application institute
The inclination angle of title, that is, actual plasma sputter line deviate the angle of vertical ion line.Form two, (b) figure institute in Fig. 1
Show, during the vertical substrate of sputter direction, such as target is in position 1, it is believed that inclination angle is 0 °, when target moves in vertical two-dimensional surface
When, it is believed that belong to inclination angle sputtering；As shown in Fig. 1 (b) figure, inclination angle of the target at position 5 is θ.Form three, such as Fig. 1 (c)
Shown in figure, during the vertical substrate of sputter direction, such as target is in position 1, it is believed that inclination angle is 0 °, when target moves in horizontal two-dimension face
When dynamic, it is believed that belong to inclination angle sputtering；As shown in Fig. 1 (c) figure, inclination angle of the target at position 5 is θ.
The principle of the titania-doped film of (004) orientation metal, present inventor are formed for inclination angle magnetron sputtering
Found by further investigation, its possible principle is, when carrying out magnetron sputtering with certain angle of inclination, can to efficiently control
The ion accumulation of short-range order, forms the column crystal of the different directions of growth in film, and then forms Anatase (004) orientation
Metal-doped titanium deoxid film.
The transparent conducting glass of the application, compared with prior art, the application (004) oriented growth on amorphous substrate
The metal-doped titanium deoxid film of (004) anatase there is higher mobility compared with the film of (101) phase oriented growth, it is conductive
Property can be enhanced about more than once, and the film lowest resistivity of Anatase (004) preferential growth of the application is up to 4.0 × 10-4
Ω·cm.Also, it the preparation method of the application, can implement on amorphous substrate, and be carried out by magnetron sputtering technique, easily
Produced in cheap large area；The transparent conducting glass preparation method of the application, can prepare Anatase (004) degree of orientation can
The transparent conductive film of tune, technical scheme is provided to continue to optimize the performance of conductive film.
The application is described in further detail below by specific embodiment.Following examples only are entered to advance to the application
One step illustrates, should not be construed as the limitation to the application.
Embodiment one
The transparent conductive film of this example, using magnetron sputtering method, with 30 ° of the inclination angle magnetron sputtering in inclination angle, prepare niobium and mix
Miscellaneous titanium dioxide film, after annealing processing is then carried out, the niobium for obtaining Anatase (004) preferential growth is titania-doped thin
Film.It is specific as follows：
(1) using titanium dioxide powder and niobium pentaoxide powder as raw material, purity 4N-5N, according to Ti：Nb mol ratios are
9.5：0.5 dispensing, by grinding after mixing, it is allowed to well mixed.The pre-burning 3h at 820 DEG C is then put into high temperature silicon molybdenum stove；
After the completion of add polymerizer polyvinyl alcohol 5mL, be pressed into that 4.5mm is thick, circular target of diameter 5cm with powder compressing machine, then
It is put into high temperature silicon molybdenum stove and 1350 DEG C of sintering 5h is risen to 5 DEG C/min, after cooling, copper back end thick fixed 0.5mm, that is, niobium is made
Titania-doped target.
(2) the titania-doped target of niobium obtained uses inclination angle magnetron sputtering technique, prepares the titania-doped film of niobium,
Wherein inclination angle is 30 °, and sputtering chamber pressure is 0.3Pa, and sputtering chamber atmosphere is argon gas, and substrate is soda-lime-silica glass, and underlayer temperature is
25 DEG C, sputtering power 0.5W/cm2, sedimentation rate 10nm/min, sputtering time 20min, prepare 200nm thickness
The titania-doped film of niobium.
(3) the after annealing processing of the titania-doped film of niobium, the titania-doped film of niobium is heated under an inert atmosphere
450 DEG C, 30min is incubated, room temperature is cooled to, obtains the titania-doped film of niobium of anatase (004) preferential growth, i.e. this example
Transparent conductive film.
The transparent conductive film prepared using X-ray diffraction to this example is detected, as a result as shown in Fig. 2 result is shown,
In transparent conductive film prepared by this example, its crystal formation is Anatase, has obvious (004) preferential growth.Crystallinity is good
Titania-doped preferentially performance it is good, crystal grain is big.Film sections are analyzed using SEM, as a result as Fig. 3 can be seen that
Crystal grain arrangement is consistent in film, has about 30 ° of inclination angle.10.5cm is obtained by Hall test instrument2/ Vs carrier mobility
Rate, carrier concentration is close to 9.0 × 1020cm-3, resistivity is 7.8 × 10-4Ω cm, also, 39.2 Ω of square resistance/sq, can
See that transparent conductive film electric conductivity prepared by this example is good.In addition, being tested by transmitted light spectrometer, obtain saturating more than 78.5%
Light rate.
Above test result is shown, the transparent conductive film of this example, can reach market matured product, such as ITO, AZO and
FTO performance indications.But the transparent conductive film of this example is the titanium deoxid film of niobium doping, its cost of raw material is cheap
Aboundresources, there is bigger cost and resources advantage, also, the preparation method of this example is simple to operation, and production cost is low, more
It is suitable for mass producing.
Embodiment two
The transparent conductive film of this example, using magnetron sputtering method, with 14 ° of inclination angle magnetron sputterings at inclination angle, prepare tantalum and mix
Miscellaneous titanium dioxide film, after annealing processing is then carried out, the tantalum for obtaining Anatase (004) phase preferential growth is titania-doped thin
Film.It is specific as follows：
(1) using titanium dioxide powder and tantalum pentoxide powder as raw material, purity 4N-5N, according to Ti：Ta mol ratios are
9.4：0.6 dispensing, by grinding after mixing, it is allowed to well mixed.The pre-burning 3h at 820 DEG C is then put into high temperature silicon molybdenum stove；
After the completion of add polymerizer polyvinyl alcohol 5mL, be pressed into that 4.5mm is thick, circular target of diameter 5cm with powder compressing machine, then
It is put into high temperature silicon molybdenum stove and 1350 DEG C of sintering 5h is risen to 5 DEG C/min, after cooling, copper back end thick fixed 0.5mm, that is, tantalum is made
Titania-doped target.
(2) the titania-doped target of tantalum obtained uses inclination angle magnetron sputtering technique, prepares the titania-doped film of tantalum,
Wherein inclination angle is 14 °, and sputtering chamber pressure is 0.3Pa, and sputtering chamber atmosphere is argon gas, and substrate is soda-lime-silica glass, and underlayer temperature is
25 DEG C, sputtering power 0.5W/cm2, sedimentation rate 10nm/min, sputtering time 40min, prepare 400nm thickness
The titania-doped film of tantalum.
(3) the after annealing processing of the titania-doped film of tantalum, the titania-doped film of tantalum is heated under an inert atmosphere
400 DEG C, 60min is incubated, room temperature is cooled to, obtains the titania-doped film of tantalum of Anatase (004) preferential growth, i.e., originally
The transparent conductive film of example.
Using the identical method of embodiment one, the transparent conductive film prepared to this example detects, as a result such as Fig. 4 institutes
Show, as a result show, its crystal formation of X-ray diffraction measure is mainly anatase, has obvious (004) phase preferential growth.Using SEM
Film sections are analyzed, as a result as Fig. 5 can be seen that in film, crystal grain arrangement is consistent, has about 14 ° of inclination angle.Hall
Tester obtains 4.2cm2/ Vs carrier mobility, carrier concentration is close to 1.2 × 1021cm-3, resistivity is 1.2 × 10-3
Ω cm, also, 30.0 Ω of square resistance/sq, transparent conductive film electric conductivity are good.
In addition, this example uses transmitted light spectrometer, respectively to annealed processing and thin without the electrically conducting transparent of annealed processing
The light transmittance of film is tested, and test result is as shown in Figure 6.As a result show, the electrically conducting transparent of the annealed processing of this example is thin
Film visible-range iuuminting rate is up to 80%, i.e. block curve 1 in Fig. 6；There is no annealed processing, that is, after the completion of sputtering not
500 DEG C of heating and thermal insulation 30min of inert atmosphere are carried out, its light transmittance is significantly less than the transparent conductive film of annealed processing, i.e. Fig. 6
In dashed curve 2；It can be seen that the transparent conductive film of this example after annealing, its light transmittance significantly improves.
It can be seen that the transparent conductive film of this example, suitable with the transparent conductive film performance of embodiment one, market can be reached
Matured product.Also, likewise, the transparent conductive film of this example is the titanium deoxid film of tantalum doping, the cost of raw material is cheap
Aboundresources, there is bigger cost and resources advantage, preparation method is simple to operation, and production cost is low, more suitable for big rule
Mould produces.
Embodiment three
The transparent conductive film of this example, using magnetron sputtering method, with 11 ° of the inclination angle magnetron sputtering in inclination angle, prepare tantalum and mix
Miscellaneous titanium dioxide film, after annealing processing is then carried out, the tantalum for obtaining Anatase (004) preferential growth is titania-doped thin
Film.It is specific as follows：
(1) using titanium dioxide powder and tantalum pentoxide powder as primary raw material, purity 4N-5N, according to Ti：Ta mol ratios
For 9：1 dispensing, by grinding after mixing, it is allowed to well mixed.The pre-burning 3h at 820 DEG C is then put into high temperature silicon molybdenum stove；It is complete
Into rear addition polymerizer polyvinyl alcohol 5mL, 4.5mm thickness, diameter 5cm circular target, Ran Houfang are pressed into powder compressing machine
Enter in high temperature silicon molybdenum stove and 1350 DEG C of sintering 5h are risen to 5 DEG C/min, after cooling, copper back end thick fixed 0.5mm, that is, tantalum is made and mixes
Miscellaneous titanium dioxide target.
(2) the titania-doped target of tantalum obtained uses inclination angle magnetron sputtering technique, prepares the titania-doped film of tantalum,
Wherein inclination angle is 11 °, and sputtering chamber pressure is 0.3Pa, and sputtering chamber atmosphere is argon gas, and substrate is soda-lime-silica glass, and underlayer temperature is
25 DEG C, sputtering power 0.5W/cm2, sedimentation rate 10nm/min, sputtering time 41min, prepare 415nm thickness
The titania-doped film of tantalum.
(3) the after annealing processing of the titania-doped film of tantalum, the titania-doped film of tantalum is heated under an inert atmosphere
400 DEG C, 60min is incubated, room temperature is cooled to, obtains the titania-doped film of tantalum of Anatase (004) preferential growth, i.e., originally
The transparent conductive film of example.
Using the identical method of embodiment one, the transparent conductive film prepared to this example detects.As a result such as Fig. 7 institutes
Show, as a result show, its crystal formation of X-ray diffraction measure is mainly anatase, has obvious (004) preferential growth.Using SEM pairs
Film sections are analyzed, and as a result as can be seen in Figure 8, crystal grain arrangement is consistent in film, has about 11 ° of inclination angle.Hall is surveyed
Try instrument and obtain 1.7cm2/ Vs carrier mobility, carrier concentration is close to 2.7 × 1021cm-3, resistivity is 1.3 × 10-3Ω
Cm, also, 32.5 Ω of square resistance/sq, transparent conductive film electric conductivity are good.In addition, visible-range iuuminting rate is up to
80%.
It can be seen that the transparent conductive film of this example, suitable with the transparent conductive film performance of embodiment one, market can be reached
Matured product.Also, likewise, the transparent conductive film of this example is the titanium deoxid film of tantalum doping, the cost of raw material is cheap
Aboundresources, there is bigger cost and resources advantage, preparation method is simple to operation, and production cost is low, more suitable for big rule
Mould produces.
Example IV
The transparent conductive film of this example, using magnetron sputtering method, with 20 ° of the inclination angle magnetron sputtering in inclination angle, prepare niobium and mix
Miscellaneous titanium dioxide film, after annealing processing is then carried out, the niobium for obtaining Anatase (004) preferential growth is titania-doped thin
Film.It is specific as follows：
(1) using titanium dioxide powder and niobium pentaoxide powder as primary raw material, purity 4N-5N, according to Ti：Nb mol ratios
For 9.5：0.5 dispensing, by grinding after mixing, it is allowed to well mixed.Then it is put into the pre-burning at 820 DEG C in high temperature silicon molybdenum stove
3h；After the completion of add polymerizer polyvinyl alcohol 5mL, be pressed into that 4.5mm is thick, circular target of diameter 5cm with powder compressing machine, so
After be put into high temperature silicon molybdenum stove 1350 DEG C of sintering 5h risen to 5 DEG C/min, after cooling, copper back end thick fixed 0.5mm, that is, be made
The titania-doped target of niobium.
(2) the titania-doped target of niobium obtained uses inclination angle magnetron sputtering technique, prepares the titania-doped film of niobium,
Wherein inclination angle is 20 °, and sputtering chamber pressure is 0.3Pa, and sputtering chamber atmosphere is argon gas, and substrate is soda-lime-silica glass, and underlayer temperature is
25 DEG C, sputtering power 0.5W/cm2, sedimentation rate 10nm/min, sputtering time 66min, prepare 660nm thickness
The titania-doped film of niobium.
(3) the after annealing processing of the titania-doped film of niobium, by the titania-doped film of niobium after chloride solution soaks,
400 DEG C are heated under an inert atmosphere, are incubated 60min, are cooled to room temperature, the niobium for obtaining Anatase (004) preferential growth is mixed
The transparent conductive film of miscellaneous titanium deoxid film, i.e. this example.
Using the identical method of embodiment one, the transparent conductive film prepared to this example detects.As a result such as Fig. 9 institutes
Show, its crystal formation of display X-ray diffraction measure is mainly anatase, has obvious (004) preferential growth.Using SEM to film
Section is analyzed, and as a result as Figure 10 can be seen that in film, crystal grain arrangement is consistent, has about 20 ° of inclination angle.Hall test instrument
Acquisition is more than 3.4cm2/ Vs carrier mobility, carrier concentration is close to 2.9 × 1021cm-3, resistivity is 6.8 × 10-4Ω
Cm, also, 10.3 Ω of square resistance/sq, transparent conductive film electric conductivity are good.In addition, visible-range iuuminting rate is up to
74.2%.
It can be seen that the transparent conductive film of this example, suitable with the transparent conductive film performance of embodiment one, market can be reached
Matured product.Also, likewise, the transparent conductive film of this example is the titanium deoxid film of niobium doping, the cost of raw material is cheap
Aboundresources, there is bigger cost and resources advantage, preparation method is simple to operation, and production cost is low, more suitable for big rule
Mould produces.
Embodiment five
This example further study shadow of the inclination angle to Anatase (004) phase oriented growth based on example IV
Ring.Specifically, this example is respectively with 1 ° of inclination angle, 5 °, 11 °, 14 °, 17 °, 20 °, 25 °, 27 °, 30 ° of inclination angle magnetron sputtering, system
The titania-doped film of standby niobium.Magnetic control target and other conditions and parameter are all identical with example IV.
Finally nine titanium deoxid films that nine angle magnetron sputterings obtain are entered using example IV identical method
Row detection, as a result as shown in table 1.
And it have detected (004) degree of orientation of nine titanium deoxid films, (004) degree of orientation η(004)Calculation formula such as
Under：
Wherein, MD(004)It is the March-Dollase coefficients that (004) is orientated in XRD refine.
Titanium deoxid film test result prepared by the different inclination angle angle of table 1
The result of table 1 shows that, with the angle increase at inclination angle, (004) degree of orientation is bigger, corresponding carrier mobility
Rate is also higher, and the electric conductivity of transparent conductive film is more preferable.When reaching 11 ° at inclination angle, (004) degree of orientation has been up to
20%, (004) XRD diffraction maximums have become the main diffraction peak of transparent conductive film；Substantially may be used in 17-25 degree at inclination angle
To ensure that (004) degree of orientation is more than 30%；When inclination angle is more than 27 °, (004) degree of orientation is even more than 50%.Tilt
The angle at angle is the transparent conductive film prepared by 11-30 degree, and its electric conductivity can meet the use of solar cell substantially
Demand.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Specific implementation please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of conceiving from the application, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. a kind of transparent conducting glass, including amorphous substrate and the transparent conductive film being attached on amorphous substrate, it is special
Sign is：The transparent conductive film is the metal-doped titanium deoxid film of Anatase (004) orientation.
2. transparent conducting glass according to claim 1, it is characterised in that：The grain growth direction row of the conductive film
Cloth is consistent.
3. transparent conducting glass according to claim 1, it is characterised in that：Mixed in the metal-doped titanium deoxid film
Miscellaneous element is niobium and/or tantalum.
4. transparent conducting glass according to claim 3, it is characterised in that：The amount of the doping of the niobium is gross weight
0.1-20%, the amount of the tantalum doping is the 0.1-20% of gross weight；Preferably, the amount of the doping of the niobium is gross weight
1.5-7%, the amount of the tantalum doping is the 1.5-7% of gross weight.
5. according to the transparent conducting glass described in claim any one of 1-4, it is characterised in that：The amorphous substrate is glass
At least one of glass, quartz, polyimides, polyethylene terephthalate and makrolon.
6. the application of transparent conducting glass in solar cells according to claim any one of 1-5.
7. the preparation method of the transparent conducting glass according to claim any one of 1-5, it is characterised in that：Including using magnetic
Control sputtering technology, sputtering power 0.5-3.0W/cm2, sputtered with the inclination angle of 1-60 degree in amorphous substrate surface,
Amorphous substrate surface forms film, and then carrying out annealing makes thin film crystallization, obtains the dioxy of Anatase (004) orientation
Change titanium film, that is, form the transparent conducting glass；The inclination angle refers to that plasma sputter line deviates vertical ion line
Angle.
8. preparation method according to claim 7, it is characterised in that：The angle at the inclination angle is 10-60 degree, preferably
11-30 degree.
9. the preparation method according to claim 7 or 8, it is characterised in that：The condition of the annealing is, in vacuum or
In inert atmosphere or reducing atmosphere, 250-650 DEG C of insulation 0-10h；Preferable annealing condition is, in vacuum or inert atmosphere
Or in reducing atmosphere, 350-400 DEG C of insulation 0.5-1h.
10. the preparation method according to claim 7 or 8, it is characterised in that：Before annealing, in addition to film
Carry out chloride solution immersion treatment, film surface deposited metal or semiconductor or high molecular polymer processing, UV ozone spoke
According at least one of processing, infrared irridiation processing.
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| CN110894138A (en) * | 2019-01-30 | 2020-03-20 | 中山大学 | Environment-friendly automobile glass |
| CN114649429A (en) * | 2022-03-15 | 2022-06-21 | 北京大学深圳研究生院 | Nickel oxide based self-bias photoelectric detector and preparation method and application thereof |
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