CN109402579A - (001) it is orientated CdS flexible extensible photo-conductive film material and preparation method thereof - Google Patents
(001) it is orientated CdS flexible extensible photo-conductive film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of flexible extensible light-sensitive material and preparation method thereof, the flexible extensible light-sensitive material includes flexible substrates, the buffer layer in flexible substrates, and the CdS film of (001) orientation on buffer layer.The described method includes: 1) prepare resistivity on a flexible substrate in the buffer layer of 5K Ω m~5M Ω m；2) CdS film of (001) orientation, and the parameter of magnetron sputtering are prepared on the buffer layer using the method for magnetron sputtering are as follows: target rifle power density is 5W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10‑4Pa, operating air pressure are 0.5Pa~10Pa；3) it anneals, obtains light-sensitive material.The present invention is prepared for having obtained the light-sensitive material of flexible extensible with the CdS film of (001) orientation, can still having kept good electric property under large scale stress tensional state, substantially increase the prospect of wearable application.
Description
Technical field
The invention belongs to the flexible optoelectronic sensing material preparation technical fields towards wearable application, are related to a kind of flexibility
Stretchable light-sensitive material and preparation method thereof, more particularly to a kind of flexible extensible photo-conductive film material with (001) orientation CdS
Material and preparation method thereof.
Background technique
With being constantly progressive for society, continuous improvement of people's living standards, the continuous quickening of rhythm of life, people are to life
The requirement of bioplasm amount is also higher and higher, and the appearance of intelligent wearable device brings new convenience to people's life, wearable to set
Ambient enviroment also can be monitored in real time to realize the monitoring to physical signs in the standby information exchange that may be implemented with organism
Index of correlation and data.Realize above functions it is necessary to have the sensor of various different function that, to obtain data, sensor is again
It inevitably needs and biological tissue, direct body contact, therefore, the sensor needs towards wearable application is simultaneous simultaneously
Information exchange ability and biological safety are cared for, this just puts forward new requirements the flexibility of sensor.
Flexible sensor is a kind of sensor opposite with rigid sensor, there is a situation where bending stretch etc. deformation
Under can still keep good sensing capabilities.
In face of the preparation of flexibility photoelectric device, many effort are had also been made in technical staff, as CN101532178A,
CN203820886U discloses flexible photosensitive material and preparation method thereof, respectively using materials such as flexible silicone rubbers as substrate, at it
It is upper that light-sensitive material is prepared using different process.These techniques tentatively realize flexibility, but do not have but can for obtained product
Tensile property can not realize conformal be bonded with skin and bodily tissue.
For photosensitive sensor, light-sensitive material is critical component therein, and photo-conductive film material is the light using semiconductor
A kind of sensor that resistance value changes with the power of incident light made of electrical effect；Incident intensity, resistance reduce, incident light
Weak, resistance increases.Light-sensitive material is generally used for the measurement of light, the control of light and photoelectric conversion and (variation of light is converted to electricity
Variation).Common photo-resistor cadmium sulfide photoresistor changes with strong and weak change of incident ray (visible light), black
Under dark condition, its resistance value (resistance in the dark) is up to the Europe 1~10M, and at intense light conditions (100LX), its resistance value (bright resistance) is only several hundred
To several thousand ohms.Photo-resistor is to the sensibility (i.e. spectral characteristic) of light and human eye to the sound of visible light (0.4~0.76) μm
It should be very close to can all cause its change in resistance as long as the light that human eye can be experienced.
At present wearable sensor be limited to material hard and photo-conductive film material sensitivity it is not high the problems such as and
It can not be widely applied, therefore a kind of preparation process of stretchable sensor material of the present invention is that wearable application solves
The problem of organ fitting and tissue are protected.
For the performance of light-sensitive material, high preferred orientation is one of the important parameter for determining performance.High preferred orientation refers to: crystal material
For material under pulverulence, the distribution of each crystal plane direction is impartial, and exposure crystal face is minimum energy crystal face, is both most stable
Crystal face.However in thin-film material, due to the difference of growth conditions, cause the surface of base material can be different, therefore expose
With the crystal face of preferred orientation just not necessarily most steady surface, such as six side CdS, in nature or in most of thin-film material
Exposed crystal face is (101).
It is relatively fewer to the research for the thin-film material for preparing specific orientation in the preparation process of CdS material, how to regulate and control
The high preferred orientation of light-sensitive material is obtained with improving flexible, stretchable device and the sensitivity of light-sensitive material in large scale strained condition
Under still the light-sensitive material of excellent performance can be kept to be of great significance, to solve that cannot achieve in the prior art can in flexibility
Stretch the problem of can still stablizing the flexible photosensitive sensing material used under use condition.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of photosensitive materials of flexible extensible
Material and preparation method thereof, more particularly to a kind of flexible extensible photo-conductive film material with (001) _ orientation CdS and its preparation
Method.Technique ginseng when present invention employs by controlling specific metal buffer layer resistance and adjust magnetron sputtering C dS film
Several methods is prepared for having obtained the light-sensitive material of flexible extensible with the CdS film of (001) orientation, having answered in large scale
Good electric property can be still kept under power tensional state, substantially increase the prospect of wearable application.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides light-sensitive material a kind of flexible and with tensile property, the light-sensitive material includes
Flexible substrates, the buffer layer in flexible substrates, and the CdS film of (001) orientation on buffer layer.
In the present invention, " light-sensitive material flexible and with tensile property " refers to: flexible extensible light-sensitive material.
Buffer layer in the present invention is metalliferous buffer layer.
The present invention provides a kind of light-sensitive material, the CdS film with (001) orientation, due to CdS crystal have it is each to
The CdS film of anisotropic feature, different orientation has different property, and specific orientation (001) orientation that the present invention obtains
CdS film has flexible extensible, and the extensibility of CdS film is greater than 10%, can still keep good under large scale deformation
Electric property.
Light-sensitive material of the invention is the flexible extensible of a kind of CdS film with specific orientation and metal composite structure
Light sensor material has novelty, is the metal and semiconductors coupling stretched with large scale found for the first time both at home and abroad
Structure light-sensitive material.
As the optimal technical scheme of light-sensitive material of the present invention, the buffer layer is existed by noble metal film and fusing point
200 DEG C of low-melting-point metal films below are constituted, and the noble metal film side of buffer layer is contacted with flexible substrates, buffer layer
Low-melting-point metal film side is contacted with CdS film.
In this optimal technical scheme, fusing point 200 DEG C or less be, for example, 200 DEG C, 180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C,
135 DEG C, 120 DEG C, 100 DEG C or 80 DEG C etc., preferably fusing point is lower than 190 DEG C.
Preferably, the noble metal film with a thickness of 2nm~30nm, such as 2nm, 4nm, 5nm, 8nm, 10nm, 12nm,
15nm, 18nm, 20nm, 22nm, 25nm, 26nm, 28nm or 30nm etc..
Preferably, the low-melting-point metal film with a thickness of 5nm~20nm, such as 5nm, 6nm, 8nm, 10nm, 13nm,
15nm, 16nm, 17nm, 18nm or 20nm etc..
Preferably, the CdS film with a thickness of 20nm~1000nm, such as 20nm, 40nm, 100nm, 150nm,
200nm、225nm、300nm、350nm、400nm、450nm、500nm、550nm、600nm、700nm、750nm、800nm、
850nm, 900nm or 1000nm etc..
Preferably, the noble metal film in the buffer layer includes any one in gold thin film, Ag films or platinum film
Or at least two combination, but be not limited to the above-mentioned noble metal film enumerated, other are commonly used in the art to can reach identical effect
The noble metal film of fruit can also be used for the present invention.
Preferably, the low-melting-point metal film in the buffer layer is work function and the matched metallic film of CdS film.
It is highly preferred that the buffer layer is by noble metal film and fusing point at 200 DEG C or less and work function is matched with CdS film
Low-melting-point metal film constitute, meet the low melting point film such as In film of above-mentioned fusing point and work function matching condition, but simultaneously
It is not limited to In film, other meet above-mentioned fusing point and the low melting point film of work function matching condition can also be used for the present invention.
In this optimal technical scheme, work function and the fine fisssure of the fusing point in 200 DEG C of low-melting-point metal films below
Line structural metal electrode matches to form Ohmic contact with the light-sensitive semiconductor material.
Preferably, the flexible substrates are high molecular polymer flexible substrates, preferably silastic material, further preferably
It is greater than 200% silastic material for extensibility.
Preferably, the thickness of the flexible substrates be no more than 0.5cm, such as 0.45cm, 0.4cm, 0.35cm, 0.32cm,
0.3cm, 0.25cm, 0.2cm or 0.1cm etc..
Second aspect, the present invention provide the preparation method of light-sensitive material as described in relation to the first aspect, the method includes with
Lower step:
(1) resistivity is prepared on a flexible substrate in the buffer layer of 5K Ω m~5M Ω m；
(2) CdS film of (001) orientation, and the work of magnetron sputtering are prepared on the buffer layer using the method for magnetron sputtering
Skill parameter are as follows: target rifle power is 5W/m2~10W/m2, such as 5W/m2、5.5W/m2、6W/m2、7W/m2、7.5W/m2、8W/m2、9W/
m2Or 10W/m2Deng；Vacuum back end air pressure is less than 9 × 10-4Pa, such as 8 × 10-4Pa、7×10-4Pa、6×10-4Pa、5×10- 4Pa、4×10-4Pa、3×10-4Pa or 2 × 10-4Pa etc.；Operating air pressure be 0.5~10Pa, such as 0.5Pa, 1Pa, 2Pa,
3.5Pa, 4.5Pa, 5Pa, 6Pa, 8Pa or 10Pa etc.；
(3) it anneals, obtains light-sensitive material flexible and with tensile property.
In step (1) of the present invention, resistivity 5K Ω m~5M Ω m of buffer layer is for example are as follows: 5K Ω m, 10K
Ω·m、75KΩ·m、125KΩ·m、150KΩ·m、200KΩ·m、245KΩ·m、300KΩ·m、360KΩ·m、
400KΩ·m、450KΩ·m、500KΩ·m、550KΩ·m、600KΩ·m、650KΩ·m、700KΩ·m、750K
Ω·m、800KΩ·m、1MΩ·m、1.2MΩ·m、1.5MΩ·m、2MΩ·m、2.2MΩ·m、3MΩ·m、3.5M
Ω m, 4M Ω m, 4.5M Ω m or 5M Ω m etc..
The present invention provides a kind of preparation processes of novel flexible photosensitive sense film material, utilize suitable technique item
Part controls the buffer layer to form specific electric resistance range 5K Ω m~5M Ω m, then the magnetic on the buffer layer of specific electric resistance
Control sputtering, and target rifle power, the air pressure of vacuum back end and operating air pressure condition are controlled, there is last low-temperature annealing (001) to take
To CdS film, realize the preparation of flexibility and stretchable light sensor film.
The CdS photo-conductive film with specific orientation with light sensing function has been prepared in method of the invention, and should
Sensing material can use under large scale strain, be greater than 10% using extensibility range.
As the optimal technical scheme of the method for the invention, step (1) described buffer layer is by noble metal film and fusing point
It is constituted in 200 DEG C of low-melting-point metal films below, and the noble metal film side of buffer layer is contacted with flexible substrates, buffer layer
Low-melting-point metal film side contacted with CdS film.
In this optimal technical scheme, by preparing noble metal/low-melting-point metal buffer layer on a flexible substrate, then buffering
The low-melting-point metal side of layer prepares the CdS film of specific orientation (001), and the photosensitive function of flexible extensible may be implemented, and
Realize the light sensor thin-film material of the lower measurement light intensity of large scale strain.
In the present invention, control to form specific electrical resistivity range 5K Ω m~5M Ω by different growth conditions
M using the buffer layer being made of magnetron sputtering preparation noble metal film and low-melting-point metal film and adjusts magnetron sputtering
Power and the technological parameters such as air pressure to adjust resistivity to required range.
As the optimal technical scheme of the method for the invention, the process of buffer layer is prepared on a flexible substrate are as follows:
(A) noble metal film is prepared by magnetron sputtering on a flexible substrate；
(B) fusing point is then prepared on noble metal film in 200 DEG C of low-melting-point metal films below, thus in flexible base
The buffer layer being made of noble metal film and low-melting-point metal film is formed on bottom.
Preferably, step (A) magnetron sputtering is direct current or rf magnetron sputtering.
Preferably, during step (A) described magnetron sputtering, target rifle power density is 1W/m2~10W/m2, such as 1W/
m2、2W/m2、3W/m2、3.5W/m2、4W/m2、5W/m2、5.5W/m2、6W/m2、7W/m2、8.5W/m2Or 10W/m2Deng；Operating air pressure
For 0.5Pa~10Pa, such as 0.5Pa, 1Pa, 2Pa, 3.5Pa, 4.5Pa, 5Pa, 6Pa, 8Pa or 10Pa etc..
Preferably, during step (A) described magnetron sputtering, vacuum back end air pressure is less than 9 × 10-3Pa, such as 8 ×
10-3Pa、、7×10-4Pa、6×10-4Pa、5×10-4Pa、4×10-4Pa、3×10-4Pa、2×10-4Pa or 1 × 10-4Pa etc..
Preferably, during step (A) described magnetron sputtering, sample stage temperature be 25 DEG C~200 DEG C, such as 25 DEG C,
35 DEG C, 50 DEG C, 65 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 135 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc..
Preferably, during step (A) described magnetron sputtering, growth time be 1s~30s, such as 1s, 3s, 4s, 5s,
6s, 8s, 10s, 12s, 14s, 16s, 18s, 20s, 23s, 25s or 30s etc..
Preferably, step (B) the low-melting-point metal film is work function and the matched metallic film of CdS film.
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and the magnetron sputtering is preferably
Magnetically controlled DC sputtering or rf magnetron sputtering.
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls following technique ginseng
Number: target rifle power is 1W/m2~3W/m2, such as 1W/m2、1.5W/m2、1.8W/m2、2W/m2、2.2W/m2、2.4W/m2、2.7W/
m2Or W/m2Deng；Operating air pressure is 0.5Pa~10Pa, such as 0.5Pa, 1Pa, 3Pa, 4Pa, 5Pa, 7Pa, 8Pa or 10Pa etc..
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls the air pressure of vacuum back end
Less than 2 × 10-3Pa, such as 1.5 × 10-3Pa、1×10-3Pa、0.5×10-3Pa or 0.2 × 10-3Pa etc..
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls sample stage temperature and be
25 DEG C~200 DEG C, such as 25 DEG C, 30 DEG C, 45 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 125 DEG C, 145 DEG C, 170 DEG C, 180 DEG C or 200 DEG C
Deng.
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls growth time and be
10s~60s, such as 10s, 20s, 25s, 35s, 40s, 50s, 55s or 60s etc..
It is above-mentioned prepare buffer layer on a flexible substrate during, the target rifle power of step (A) and (B) described magnetron sputtering
It is the most critical parameters of adjustment buffering layer resistivity with operating air pressure, is conducive to accurately control buffering layer resistivity in 5K Ω m
~5M Ω m.
In step (2) of the present invention, the magnetron sputtering used when preparing the CdS film of (001) orientation is radio frequency magnetron
Sputtering.
Preferably, during step (2) prepares the CdS film that (001) is orientated using the method for magnetron sputtering, sample stage
Temperature be 25 DEG C~200 DEG C, such as 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 125 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 165 DEG C, 180 DEG C or 200 DEG C etc..
As the optimal technical scheme of the method for the invention, step (2) prepares (001) using the method for magnetron sputtering and takes
To CdS film during, growth time is preferably 80s~500s, for example, 80s, 100s, 125s, 140s, 160s, 185s,
200s, 220s, 245s, 280s, 320s, 350s, 375s, 400s, 450s or 500s etc..
As the optimal technical scheme of the method for the invention, step (3) annealing is in Ar gas and/or N2Under protection into
Row.
" Ar gas and/or N of the present invention2" refer to: it can be Ar gas, be also possible to N2, can also be Ar gas and N2Mixing
Gas.
Preferably, the temperature of step (3) described annealing is 150 DEG C~200 DEG C, such as 150 DEG C, 160 DEG C, 165 DEG C, 175
DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc..
Preferably, the time of step (3) described annealing be 10min, 15min, 18min, 20min, 22min, 24min,
25min, 27min, 28min or 30min etc..
As the further preferred technical solution of the method for the invention, it the described method comprises the following steps that (preparation is flexible
The process flow diagram of stretchable light-sensitive material is referring to Fig. 1):
(1) resistivity is prepared on a flexible substrate in the buffer layer of 5K Ω m~5M Ω m, and the buffer layer is by your gold
Belong to film and fusing point to constitute in 200 DEG C of low-melting-point metal films below, and the noble metal film side of buffer layer and flexible base
Bottom contact, detailed process are as follows:
(A) noble metal film layer, the work of magnetron sputtering are prepared by magnetron sputtering in high molecular polymer flexible substrates
Skill parameter are as follows: target rifle power density is 1W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10-3Pa, operating air pressure 0.5Pa
~10Pa, sample stage temperature are 25 DEG C~200 DEG C, and growth time is 1s~30s；
(B) fusing point is then prepared in 200 DEG C of low-melting-point metal films below by magnetron sputtering on noble metal film
Layer, the parameter of magnetron sputtering are as follows: target rifle power is 1W/m2~3W/m2, vacuum back end air pressure is less than 2 × 10-3Pa, operating air pressure
For 0.5Pa~10Pa, sample stage temperature is 25 DEG C~200 DEG C, and growth time is 10s~60s, thus soft in high molecular polymer
Property substrate on form the buffer layer that is made of noble metal film and low-melting-point metal film, the resistivity of the buffer layer is in 5K Ω
M~5M Ω m.
(2) CdS film of (001) orientation is prepared on the buffer layer using the method for rf magnetron sputtering, radio frequency magnetron splashes
The technological parameter penetrated are as follows: target rifle power density is 5W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10-4Pa, operating air pressure
For 0.5Pa~10Pa.
(3) it under Ar protection, in 150 DEG C~200 DEG C annealing (i.e. low-temperature annealing), obtains flexible and with tensile property
Light-sensitive material, i.e. flexible extensible light-sensitive material (its structural schematic diagram is referring to fig. 2).
This optimal technical scheme is by first preparing noble metal film by magnetron sputtering on a flexible substrate, then in your gold
Belong to preparation work function matching on film and low-melting-point metal is to form noble metal/low-melting-point metal buffer layer, adjusts magnetron sputtering
Technological parameter so that the resistivity of buffer layer utilizes magnetic under the specific resistivity conditions in 5K Ω m~5M Ω m
Control sputters and adjusts the parameters such as suitable target rifle power, the air pressure of vacuum back end and operating air pressure and has been prepared with specific
(001) the CdS film material being orientated, realizing finally by low-temperature annealing has the photo-conductive film material of tensility energy.
Compared with the prior art, the invention has the following beneficial effects:
1. work when present invention employs by controlling specific metal buffer layer resistance and adjust magnetron sputtering C dS film
The method of skill parameter is prepared for the light-sensitive material of flexible extensible having been obtained, in big ruler with the CdS film of (001) orientation
Good electric property can be still kept under degree stress tensional state, substantially increases the prospect of wearable application.
2. the present invention is used as buffer layer, work function matching using the matched low-melting-point metal of work function and noble metal are compound
Low-melting-point metal play the role of interface optimization between noble metal and CdS, make to form Ohmic contact between metal and CdS
Namely low resistance contact can greatly improve the electric property of sensor, realize that better photosensitive property is beaten for sensing material
Basis is descended.
3. the present invention provides it is a kind of can metal and the compound technique for obtaining flexible sensing material of CdS under cryogenic,
This provides important Technical Reference for flexible sensor preparation field.
4. the present invention is prepared for the CdS film with (001) orientation by controlling growth conditions, this has specific for preparation
The CdS film technique of orientation provides important Technical Reference.
Detailed description of the invention
Fig. 1 is the process flow diagram of present invention preparation flexible extensible light-sensitive material.
Fig. 2 is the structural schematic diagram of flexible extensible light-sensitive material prepared by the present invention, wherein 1 represents high molecular polymerization
Object flexible substrates, 2 represent layer of precious metal, and 3 represent low-melting-point metal layer, and 4 represent the CdS film of (001) orientation.
Fig. 3 is the XRD spectrum of prepared sample in embodiment 1.
Fig. 4 is the SEM image of prepared sample in embodiment 1.
Fig. 5 is the XRD spectrum of prepared sample in embodiment 2.
Fig. 6 is the SEM image of prepared sample in embodiment 2.
Fig. 7 is the XRD spectrum of prepared sample in comparative example 1.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
Gold thin film is prepared by magnetron sputtering first in PDMS substrate, the technique for preparing gold thin film is splashed for direct magnetic control
It penetrates, target rifle power is 5W/m2, vacuum back end air pressure is 5 × 10-3Pa, operating air pressure 3Pa, sample stage temperature are 25 DEG C, growth
Time is 5s, and gained Au film thickness is 10nm.
Then preparation work function is matched with CdS in gold thin film and low-melting-point metal In is made with forming Au/In buffer layer
The technique of standby In film is magnetically controlled DC sputtering, and target rifle power is 2W/m2, vacuum back end air pressure is 2 × 10-3Pa, operating air pressure
For 1Pa, sample stage temperature is 35 DEG C, growth time 20s, and gained In film thickness is 15nm.Final gained Au/In buffer layer
Resistivity be 8K Ω m.
Magnetron sputtering is recycled to prepare CdS film on Au/In buffer layer, gained film is the CdS being orientated with (001)
Thin-film material.Preparation process is rf magnetron sputtering, and target rifle power is 5W/m2, vacuum back end air pressure is 5 × 10-4Pa, work gas
Pressure is 0.5Pa, and sample stage temperature is 100 DEG C, growth time 300s.
Finally under Ar gas shielded, anneal 20min under the conditions of 180 DEG C, makes to be formed between CdS film and buffer layer good
Ohmic contact, obtain extensibility be more than 10% flexible extensible have (001) be orientated photosensitive CdS film material.
Fig. 3 is the XRD spectrum of sample prepared by the present embodiment 1, and as seen from the figure, which is orientated with (002), (002)
It (001) is parallel crystal face of equal value.
Fig. 4 is the SEM image of sample prepared by the present embodiment 1, and as seen from the figure, prepared cadmium sulphide membrane has
The characteristics of SK growth pattern, was both first grown based on island growth when reaching certain thickness with laminar mode, Jin Erzai
So on circulate with island pattern growth.It can be seen that prepared thin-film material has good consistency in figure, and
Homogeneity is good.
Embodiment 2
Platinum film is prepared by magnetron sputtering in rubber substrate first, the technique for preparing platinum film is splashed for direct magnetic control
It penetrates, target rifle power is 4W/m2, vacuum back end air pressure is 5 × 10-3Pa, operating air pressure 2Pa, sample stage temperature are 25 DEG C, growth
Time is 3s, and gained Pt film thickness is 12nm.
Then preparation work function is matched with CdS on Pt film and low-melting-point metal In is made with forming Pt/In buffer layer
The technique of standby In film is magnetically controlled DC sputtering, and target rifle power is 3W/m2, vacuum back end air pressure is 1 × 10-3Pa, operating air pressure
For 0.8Pa, sample stage temperature is 30 DEG C, growth time 22s, and gained In film thickness is 20nm.Final gained Pt/In buffering
The resistivity of layer is 1M Ω m.
Magnetron sputtering is recycled to prepare CdS film on Pt/In buffer layer, gained film is the CdS being orientated with (001)
Thin-film material.Preparation process is rf magnetron sputtering, and target rifle power is 6W/m2, vacuum back end air pressure is 2 × 10-4Pa, work gas
Pressure is 0.7Pa, and sample stage temperature is 80 DEG C, growth time 240s.
Finally under Ar gas shielded, anneal 10min under the conditions of 190 DEG C, makes to be formed between CdS film and buffer layer good
Ohmic contact, obtain extensibility be more than 10% flexible extensible have (001) be orientated photosensitive CdS film material.
Fig. 5 is the XRD spectrum of sample prepared by the present embodiment 2, and as seen from the figure, which is orientated with (002), (002)
It (001) is parallel crystal face of equal value.
Fig. 6 is the SEM image of sample prepared by the present embodiment 2, and as seen from the figure, prepared cadmium sulphide membrane has
The characteristics of SK growth pattern, was both first grown based on island growth when reaching certain thickness with laminar mode, Jin Erzai
So on circulate with island pattern growth.It can be seen that prepared thin-film material has good consistency in figure, and
Homogeneity is good.
Embodiment 3
Ag films are prepared by magnetron sputtering in PDMS substrate first, the technique for preparing gold thin film is splashed for radio frequency magnetron
It penetrates, target rifle power is 8W/m2, vacuum back end air pressure is 4 × 10-3Pa, operating air pressure 5Pa, sample stage temperature are 30 DEG C, growth
Time is 20s, and gained Ag film thickness is 10nm.
Then preparation work function is matched with CdS on Ag films and low-melting-point metal In is made with forming Ag/In buffer layer
The technique of standby In film is magnetically controlled DC sputtering, and target rifle power is 1W/m2, vacuum back end air pressure is 1.5 × 10-3Pa, work gas
Pressure is 3Pa, and sample stage temperature is 40 DEG C, growth time 30s, and gained In film thickness is 20nm.Final gained Ag/In buffering
The resistivity of layer is 0.8M Ω m.
Magnetron sputtering is recycled to prepare CdS film on Ag/In buffer layer, gained film is the CdS being orientated with (001)
Thin-film material.Preparation process is rf magnetron sputtering, and target rifle power is 7.5W/m2, vacuum back end air pressure is 6.5 × 10-4Pa, work
Making air pressure is 7Pa, and sample stage temperature is 50 DEG C, growth time 150s.
Finally under Ar gas shielded, anneal 25min under the conditions of 155 DEG C, makes to be formed between CdS film and buffer layer good
Ohmic contact, obtain extensibility be more than 10% flexible extensible have (001) be orientated photosensitive CdS film material.
Embodiment 4
Platinum film is prepared by magnetron sputtering in rubber substrate first, the technique for preparing platinum film is splashed for direct magnetic control
It penetrates, target rifle power is 10W/m2, vacuum back end air pressure is 8 × 10-3Pa, operating air pressure 10Pa, sample stage temperature is 60 DEG C, raw
It is for a long time 30s, gained Pt film thickness is 20nm.
Then preparation work function is matched with CdS on Pt film and low-melting-point metal In is made with forming Pt/In buffer layer
The technique of standby In film is magnetically controlled DC sputtering, and target rifle power is 1.5W/m2, vacuum back end air pressure is 0.5 × 10-3Pa, work
Air pressure is 9Pa, and sample stage temperature is 120 DEG C, growth time 10s, and gained In film thickness is 10nm.Final gained Pt/In
The resistivity of buffer layer is 1.5M Ω m.
Magnetron sputtering is recycled to prepare CdS film on Pt/In buffer layer, gained film is the CdS being orientated with (001)
Thin-film material.Preparation process is rf magnetron sputtering, and target rifle power is 10W/m2, vacuum back end air pressure is 8 × 10-4Pa, work
Air pressure is 8.5Pa, and sample stage temperature is 150 DEG C, growth time 400s.
Finally in N2Under protection, anneal 10min under the conditions of 200 DEG C, makes to be formed between CdS film and buffer layer good
Ohmic contact, obtaining extensibility is more than that 10% flexible extensible has the photosensitive CdS film material of (001) orientation.
Embodiment 5
Gold thin film is prepared by magnetron sputtering first in high molecular polymer flexible substrates, the technique for preparing gold thin film is
Magnetically controlled DC sputtering, target rifle power are 1.5W/m2, vacuum back end air pressure is 1.5 × 10-3Pa, operating air pressure 1Pa, sample stage
Temperature is 135 DEG C, growth time 2s, and gained Au film thickness is 4nm.
Then preparation work function is matched with CdS on Au film and low-melting-point metal In is made with forming Au/In buffer layer
The technique of standby In film is magnetically controlled DC sputtering, and target rifle power is 2.5W/m2, vacuum back end air pressure is 1.2 × 10-3Pa, work
Air pressure is 5Pa, and sample stage temperature is 160 DEG C, growth time 45s, and gained In film thickness is 19nm.Final gained Au/In
The resistivity of buffer layer is 1.8M Ω m.
Magnetron sputtering is recycled to prepare CdS film on Au/In buffer layer, gained film is the CdS being orientated with (001)
Thin-film material.Preparation process is rf magnetron sputtering, and target rifle power is 8.5W/m2, vacuum back end air pressure is 4 × 10-4Pa, work
Air pressure is 10Pa, and sample stage temperature is 185 DEG C, growth time 200s.
Finally under Ar gas shielded, anneal 15min under the conditions of 175 DEG C, makes to be formed between CdS film and buffer layer good
Ohmic contact, obtain extensibility be more than 10% flexible extensible have (001) be orientated photosensitive CdS film material.
Comparative example 1
In addition to the resistivity of control Au/In buffer layer is 1K Ω m, other preparation methods and condition are same as Example 1.
Fig. 7 is the XRD spectrum of sample prepared by this comparative example 1, it can be seen that working as buffer layer resistance value mistake from XRD diagram picture
When small, prepared sample is (100) orientation.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. light-sensitive material a kind of flexible and with tensile property, which is characterized in that the light-sensitive material includes flexible substrates, position
The CdS film of (001) orientation in the buffer layer in flexible substrates, and on buffer layer.
2. light-sensitive material according to claim 1, which is characterized in that the buffer layer is existed by noble metal film and fusing point
200 DEG C of low-melting-point metal films below are constituted, and the noble metal film side of buffer layer is contacted with flexible substrates, buffer layer
Low-melting-point metal film side is contacted with CdS film；
Preferably, the noble metal film with a thickness of 2nm~30nm；
Preferably, the low-melting-point metal film with a thickness of 5nm~20nm；
Preferably, the CdS film with a thickness of 20nm~1000nm；
Preferably, the low-melting-point metal film in the buffer layer is work function and the matched metallic film of CdS film；
Preferably, the low-melting-point metal film in the buffer layer is indium film.
3. light-sensitive material according to claim 1 or 2, which is characterized in that the flexible substrates are that high molecular polymer is soft
Property substrate, preferably silastic material, further preferably extensibility be greater than 200% silastic material；
Preferably, the thickness of the flexible substrates is no more than 0.5cm；
Preferably, the extensibility of the CdS film is greater than 10%.
4. the preparation method of light-sensitive material as described in any one of claims 1-3, which is characterized in that the method includes following
Step:
(1) resistivity is prepared on a flexible substrate in the buffer layer of 5K Ω m~5M Ω m；
(2) CdS film of (001) orientation, and the technique ginseng of magnetron sputtering are prepared on the buffer layer using the method for magnetron sputtering
Number are as follows: target rifle power density is 5W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10-4Pa, operating air pressure be 0.5Pa~
10Pa；
(3) it anneals, obtains light-sensitive material flexible and with tensile property.
5. according to the method described in claim 4, it is characterized in that, step (1) described buffer layer is by noble metal film and fusing point
It is constituted in 200 DEG C of low-melting-point metal films below, and the noble metal film side of buffer layer is contacted with flexible substrates, buffer layer
Low-melting-point metal film side contacted with CdS.
6. method according to claim 4 or 5, which is characterized in that step (1) prepares the mistake of buffer layer on a flexible substrate
Journey are as follows:
(A) noble metal film is prepared by magnetron sputtering on a flexible substrate；
(B) fusing point is then prepared on noble metal film in 200 DEG C of low-melting-point metal films below, thus on a flexible substrate
Form the buffer layer being made of noble metal film and low-melting-point metal film.
7. according to the method described in claim 6, it is characterized in that, step (A) magnetron sputtering is direct current or radio frequency magnetron
Sputtering；
Preferably, during step (A) described magnetron sputtering, target rifle power density is 1W/m2~10W/m2, operating air pressure is
0.5Pa~10Pa；
Preferably, during step (A) described magnetron sputtering, vacuum back end air pressure is less than 9 × 10-3Pa；
Preferably, during step (A) described magnetron sputtering, sample stage temperature is 25 DEG C~200 DEG C, and growth time is preferably
1s~30s.
8. method according to claim 6 or 7, which is characterized in that step (B) the low-melting-point metal film is work function
With the matched metallic film of CdS film；
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and the magnetron sputtering is preferably direct current
Or rf magnetron sputtering；
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls following technological parameter: target
Rifle power is 1W/m2~3W/m2, operating air pressure is 0.5Pa~10Pa；
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls the air pressure of vacuum back end and be less than
2×10-3Pa；
Preferably, step (B) prepares low-melting-point metal film using the method for magnetron sputtering, and controls following technological parameter: sample
Sample platform temperature is 25 DEG C~200 DEG C, and growth time is preferably 10s~60s.
9. according to the described in any item methods of claim 4-8, which is characterized in that the CdS that step (2) prepares (001) orientation is thin
The magnetron sputtering used when film is rf magnetron sputtering；
Preferably, during step (2) prepares the CdS film that (001) is orientated using the method for magnetron sputtering, sample stage temperature
It is 25 DEG C~200 DEG C, growth time is preferably 80s~500s；
Preferably, step (3) annealing is in Ar gas and/or N2Protection is lower to be carried out；
Preferably, the temperature of step (3) described annealing is 150 DEG C~200 DEG C；
Preferably, the time of step (3) described annealing is 10min~30min.
10. according to the method described in claim 4, it is characterized in that, the described method comprises the following steps:
(1) resistivity is prepared on a flexible substrate in the buffer layer of 5K Ω m~5M Ω m, and the buffer layer is thin by noble metal
Film and fusing point are constituted in 200 DEG C of low-melting-point metal films below, and the noble metal film side of buffer layer connects with flexible substrates
Touching, detailed process are as follows:
(A) noble metal film, the technological parameter of magnetron sputtering are prepared by magnetron sputtering on a flexible substrate are as follows: target rifle power is close
Degree is 1W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10-3Pa, operating air pressure are 0.5Pa~10Pa, and sample stage temperature is
25 DEG C~200 DEG C, growth time is 1s~30s；
(B) fusing point is then prepared in 200 DEG C of low-melting-point metal films below, magnetic control by magnetron sputtering on noble metal film
The parameter of sputtering are as follows: target rifle power is 1W/m2~3W/m2, vacuum back end air pressure is less than 2 × 10-3Pa, operating air pressure 0.5Pa
~10Pa, sample stage temperature are 25 DEG C~200 DEG C, and growth time is 10s~60s, to formed on a flexible substrate by your gold
Belong to the buffer layer that film and low-melting-point metal film are constituted, the resistivity of the buffer layer is in 5K Ω m~5M Ω m；
(2) CdS film of (001) orientation is prepared on the buffer layer using the method for rf magnetron sputtering, rf magnetron sputtering
Technological parameter are as follows: target rifle power density is 5W/m2~10W/m2, vacuum back end air pressure is less than 9 × 10-4Pa, operating air pressure are
0.5Pa~10Pa；
(3) it under Ar protection, anneals at 150 DEG C~200 DEG C, obtains light-sensitive material flexible and with tensile property.
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| CN101698963A (en) * | 2009-10-30 | 2010-04-28 | 陕西科技大学 | Method for preparing CdS film in microwave hydrothermal mode |
| CN102037152A (en) * | 2008-03-26 | 2011-04-27 | 索莱克山特公司 | Improved junctions in substrate solar cells |
| CN102212780A (en) * | 2011-05-04 | 2011-10-12 | 四川大学 | Method for preparing p-type cadmium sulfide film |
| CN102800719A (en) * | 2012-07-27 | 2012-11-28 | 中国科学院电工研究所 | Flexible CdTe thin-film solar cell and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037152A (en) * | 2008-03-26 | 2011-04-27 | 索莱克山特公司 | Improved junctions in substrate solar cells |
| CN101698963A (en) * | 2009-10-30 | 2010-04-28 | 陕西科技大学 | Method for preparing CdS film in microwave hydrothermal mode |
| CN102212780A (en) * | 2011-05-04 | 2011-10-12 | 四川大学 | Method for preparing p-type cadmium sulfide film |
| CN102800719A (en) * | 2012-07-27 | 2012-11-28 | 中国科学院电工研究所 | Flexible CdTe thin-film solar cell and preparation method thereof |
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