CN102169960B - Preparation method of thin film transistor of flexible electronic device - Google Patents
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Abstract
The invention provides a preparation method of a thin film transistor of a flexible electronic device. The method comprises the following steps of: (1) preparing a bendable and stretchable substrate; (2) stretching the substrate, and coating an adhesive on a surface of a stretched rubber substrate; (3) depositing a gate on the substrate; (4) depositing an organic dielectric layer unit on the device which is processed in the step (3); (5) respectively depositing a source unit layer and a drain unit layer on the organic dielectric layer unit; (6) loosening the substrate, releasing loads which are acted on the substrate, and carrying out heat treatment to eliminate an interface stress and a pressure stress of the device; and (7) depositing the organic dielectric layer unit. The invention provides the method for mechanically stretching the substrate, so the channel width of the device is reduced, manufacturing accuracy is improved effectively, and the resolution ratio of the flexible electronic device is improved.
Description
Technical field
The invention belongs to flexible electronic device manufacturing technology field, particularly a kind of solubilize manufacture method of thin film transistor of flexible electronic device.
Background technology
It is integrated that the glass plate base of based thin film transistor (TFT) or the electronic system of fexible film base constantly tend to large tracts of land, size meets or exceeds 1 meter, form so-called flexible electronics system, its outstanding feature is: cost is low, lightweight, thin form, good pliability is arranged, in order to be convenient for carrying, these devices often need curling.Yet the conventional electrical device is the semiconductor chip that is formed by silicon wafer, and self can't realize bending, damages easily in actual use.Take the large area flexible film as base plate structure organic or inorganic electronic device, be regarded as the power of electronic system future development, the application that this large-area flexible electronics system is given prominence at present the most comprises flexible flexible display, is applied to the Electronic Paper of e-book, thin-film solar cells, flexible memory circuit etc.
The flexible electronic device manufacturing process of following main flow must embody low temperature, normal atmospheric pressure, continuous feature of making, to reach the requirement of large format, low cost, high production capacity.The most key in the flexible electronic manufacturing is the Patternized technique of micro-structural, and the resolution of prepared pattern directly has influence on performance of devices.The patterning techniques that receives in the world at present larger concern comprises: photoetching technique, inkjet printing, micro-contact printing, nano impression, dip in the technology such as pen, laser direct-writing.Photoetching homenergic bundle technology is used widely in the microelectronic component patterning, resolution is high, but because its complex technical process, apparatus expensive, solvent and developer can't be used for plastic base, in addition expense material consuming time, be only applicable to the small size patterning, environmental requirement is harsh when the etching bottom, can destroy the activity of organic electronic material and polymeric substrates etc. when removing photoresist, limited in the flexible electronic Application in manufacture.Even adopt, also often be combined with transfer printing technology, the structure plan after the silica-based upper photoetching formation is transferred on the flexible base, board by transfer printing technology.The step of stripping semiconductor chip and to transfer to the rate of finished products of flexible base, board step very low from the silicon wafer, and increased manufacturing cost.Adopt the solution Patternized technique, can effectively avoid above deficiency.
Solution Patternized technique and flexible electronic have good compatibility, and make combination with reel-to-reel, can realize the manufacturing of high-efficiency and low-cost, but the pattern resolution that these techniques generate are lower, has greatly affected performance of devices.Adopting in the methods such as micro-contact printing, nano impression needs constantly to adopt photoetching making high accuracy seal, the increase that this is invisible use cost.The present invention will describe as an example of the inkjet printing technique in the solution Patternized technique example.Inkjet printing is a kind of good technique of directly writing, and can realize the one step realization of two technical processs of thin film deposition and patterning, can make combination with reel-to-reel, is considered to a kind of high efficiency, microfabrication technology cheaply.Thereby existing inkjet technology is multiplex in the printing manufacturing of PCB circuit board, can't satisfy the requirement of the high-resolution manufacturing of high-performance flexible electronics.Patent of invention CN 1425204A adopts traditional ink-jet printer deposition materials on the chosen position of substrate, in a plurality of transistor solution manufacturings, the second surface zone for the solvent matters ground of selecting than the large repulsive force in first surface zone, obtain user-defined channel width, but minimum widith only is 5 microns.Can't further reduce.Thereby existing inkjet technology can't satisfy the requirement of the high-resolution manufacturing of high-performance flexible electronics.
Concrete not enough as follows:
(1) resolution of inkjet printing technique is lower, usually at 20～50 microns, because the factors such as solution surface tension are difficult to further improve print resolution, is only applicable to the low performance electronic device;
(2) drying and the solidification process of printing solution so that the variation of volume can appear in the micro-nano structure after being shaped, can cause the internal stress of structure, even crackle occur, have reduced reliability of structure.
(3) the metal nanoparticle solution of inkjet printing forms conductor structure behind the dry solidification, but because the volatilization of solvent causes to have a large amount of spaces in the structure, is difficult to reach the electric conductivity of conventional bulk metal.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of thin film transistor of flexible electronic device, adopt the solution Patternized technique with on the elastic caoutchouc substrate of liquid deposition under the extended state, then release substrate strain, and carry out Technology for Heating Processing, can realize reducing the purpose of channel dimensions, raising device performance and the structural reliability of thin-film transistor.
The technical scheme that adopts for achieving the above object is:
(1) prepared substrate unit, described base board unit can be realized bending and stretching;
(2) stretching substrate stretches more than 50% usually, and at base board unit surface-coated adhesive, the glass transition temperature of adhesive is lower than the glass transition temperature of rubber base board unit;
(3) the some functional layers of deposition unit on the rubber base board unit, as typical TFT device, functional layer unit 2 comprises insulating barrier, semiconductor layer, grid layer, source layer, drain electrode layer etc., performance of devices depends on the critical sizes such as channel length of device;
(4) lax substrate after deposition source layer and drain electrode layer progressively discharges the elongation strain of rubber base board unit, so that the rubber base board unit restores to the original state.Heat-treat, wherein heat treatment temperature is controlled at and is lower than rubber-based glass sheet attitude conversion temperature, is higher than adhesive glass attitude conversion temperature again.So that produce relative slippage between functional layer unit and the rubber base board unit, reduce the critical size of electronic device micro-structural;
(5) the whole device for preparing previously is attached on the attachment base unit, the attachment base unit can be plastic base, flexible thin glass substrate and flexible Thin Stainless Steel plate base, is used for the distortion of the rear device of restriction shaping, keeps the stable of size.
Above step is for typical TFT structure, if also have other functional layer on the source layer, drain electrode layer, deposits after to be heated again.
To achieve these goals, the substrate of flexible electronic device of the present invention is the rubber substrate, can realize larger elastic stretching distortion (as more than 50%), still can restore to the original state behind the release external load.
To achieve these goals, the rubber substrate surface need to apply the very thin adhesive layer of one deck, realizes the bonding of substrate and functional layer.
To achieve these goals, functional layer is prepared from by solution Patternized technique (such as inkjet printing technique), requires the glass transition temperature of substrate and device function layer to be higher than the glass transition temperature of adhesive layer and the melting temperature of nano particle.
To achieve these goals, the rubber substrate need to have enough intensity, and the Thickness of rubber substrate can reference
So that discharging external load after the rubber substrate deposition functional layer can restore to the original state as much as possible.H wherein
sAnd E
sBe respectively thickness and the modulus of elasticity of rubber substrate 4, h
fAnd E
fBe respectively thickness and the modulus of elasticity of deposition function film.
To achieve these goals, the present invention is directed to full organic electronic device, the solution that adopts is insulator PVP solution, conductor PEDOT:PSS solution, semiconductor F8T2 solution; Conductor adopts metal nanoparticle solution (particle diameter is less than 50nm) in the organic and inorganic mixed electronic device.
To achieve these goals, after the functional layer deposition is finished, need to progressively discharge the strain of rubber substrate, so that the rubber substrate can partly bounce back, before not heat-treating, can reduce for the first time the channel dimensions of device.
To achieve these goals, need to further heat-treat.For full organic electronic device, utilize adhesive layer than the characteristics of low glass state conversion temperature, can under 150 ℃ of conditions, carry out glass transition, so that device layer can produce relative slippage with the rubber substrate.For the organic and inorganic electronic device, needing increases a step, under rubber substrate tensile state, utilize the low-melting characteristics of nano particle, can under 150 ℃-200 ℃, melt, form the conductor of satisfactory electrical conductivity, improve the compactness of material, improve the conductivity of structure; Then adopt the same Technology for Heating Processing with organic electronic device.This can reduce the channel dimensions of device for the second time.
To achieve these goals, the Patternized technique of functional layer can also adopt the soft etching technics such as micro-contact printing, nano-imprint process, silk-screen printing technique, the suitable techniques such as electric liquid fluid dynamic jet printing technique.
For achieving the above object, aforesaid flexible electronic device raceway groove reduction is calculated such as Fig. 3.For element length device under the extended state, i.e. element length L=source width W are got in calculating
1+ drain width W
2+ channel width W
3If former extensibility is 100%, then recover under the unstretched state, then element length l ≈ 0.5L; And because source electrode and drain electrode film bear certain pressure, so that behind the rubber substrate retraction, source width
Drain width
Channel width after can obtaining bouncing back:
Preparation method of the present invention can be used for following electronic device:
(1) large area flexible transducer, such as electronics skin, but sense temperature, pressure etc.;
(2) thin-film solar cells can effectively improve the manufacturing efficient of traditional silicon based thin film solar, reduces production costs.
The retina manufacturing of (3) Varifocal zoom lens---electronic eyes can realize the automatic focusing to the dynamic change object, is different from the traditional optical focusing, can realize being similar to the focal modes of eyeball, and when accurately focusing, shared space does not change.
The manufacture method of thin film transistor of flexible electronic device of the present invention has the inherent characteristics of similar inkjet printing, comprising:
(1) be a kind of contactless, without pressure, without the print reproduction technology of forme, it has the feature without the version digital printing, at room temperature solution is directly write and is realized the digitlization flexible printing, has simplified manufacture process.
(2) environment is not had harsh requirement, be suitable for low cost, large tracts of land, batchprocess, low temperature, contactless, " addition " technique.
(3) pattern quality is not limited by the photoetching focal length, can carry out patterning at non-planar surfaces even zanjon structure;
(4) directly utilize CAD/CAM data processing device, can realize large tracts of land dynamic alignment and in real time adjustment;
(5) need not (DOD) technology that prints on demand of physical mask;
(6) as contactless patterning techniques, can effectively reduce flaw, and can utilize the defectives such as dummy mask compensation stratified deformation, dislocation;
(7) because the structure that nano metal particles forms can be along with substrate together Stepwize Shrink, advance the density that can improve functional layer after the Overheating Treatment;
(8) if the in advance extensibility of substrate is 100%, the channel width that then realizes by this method is reduced into half of conventional method.Can be slightly less than substrate if consider the shrinkage of structure, and the relative slippage between substrate and the functional layer, then the channel width that realizes of this method can be less than half of conventional method.
The advantage of this method is that the method by a kind of mechanical stretching substrate reduces the critical size of device, has further improved resolution on the basis of inkjet printing technique resolution.
Description of drawings
By with reference to figures 1 through 4 detailed description of the invention, the above-mentioned purpose of the present invention, characteristics and advantage will become more apparent.
Fig. 1 is manufacturing principle schematic of the present invention;
Fig. 2 is for calculating the schematic diagram of raceway groove reduction;
Fig. 3 is the technical process schematic diagram that the present invention makes full OTFT;
Fig. 4 is the technical process schematic diagram that the present invention makes the organic and inorganic thin-film transistor.
Number in the figure represents respectively: 1, flexible base, board (such as plastic base, flexible thin glass substrate, flexible stainless steel foil substrate etc.); 2, micro-structural 1; 3, micro-structural 2; 4, rubber substrate; 5, attachment base (such as plastic base, flexible thin glass substrate, flexible stainless steel foil substrate etc.); 6, grid; 7, insulating barrier; 8, source electrode; 9, drain electrode; 10, semiconductor active layer; 11, metal nanoparticle source electrode; 12, metal nanoparticle drain electrode; 111, metal blocks source electrode; 121, metal blocks drain electrode.
Embodiment
The purpose of this invention is to provide a kind of thin film transistor of flexible electronic device preparation method, adopt inkjet printing technique with on the elastic caoutchouc substrate of liquid deposition under the extended state, then release substrate strain, and carry out Technology for Heating Processing, the purpose that can realize reducing the electronic device channel dimensions, improves device performance and reliability.
Embodiment 1
Fig. 3 is the technical process schematic diagram of the full OTFT of the preparation of the embodiment of the invention 1 (TFT), and as we know from the figure, preparation process of the present invention is:
(1) the prepared substrate unit 4, and base board unit is the rubber substrate, can realize bending and stretching;
The rubber substrate that the flexible base, board selection has the higher elasticity deformability requires to surpass 50% elastic strain, still can restore to the original state after the release applied external force.
(2) stretch and surface treatment for base board unit, usually stretch more than 50%, the surface-coated adhesive;
For achieving the above object, the rubber substrate need to have enough intensity, and the Thickness of rubber substrate can reference
So that discharging external load after the rubber substrate deposition functional layer can restore to the original state as much as possible.
(3) deposit grid at substrate;
At the adhesive layer of rubber substrate surface-coated one deck than the low glass state conversion temperature, to realize the bonding of substrate and functional layer.The glass transition temperature of requirement substrate and device function layer is higher than the glass transition temperature of adhesive layer.
(4) the organic dielectric layer of deposition unit 7;
(5) the drain electrode unit 9 of the source cell 8 of deposited polymer material and polymeric material;
Order according to electronic device (thin-film transistor) the structure function layer that designs is carried out inkjet printing, forms pattern.The glass transition temperature of requirement device function layer is higher than the glass transition temperature of adhesive layer.
(6) substrate is lax heat-treats
A) need progressively to discharge the load that originally acted on the substrate, so that substrate can be in recovered part distortion under the free state, this moment, functional layer was born pressure.Before not heat-treating, can reduce for the first time the channel dimensions of device.
B) heat treatment process.Utilize adhesive layer than the characteristics of low glass state conversion temperature, heat treatment temperature is controlled at and is lower than substrate and device function layer glass transition temperature, is higher than under the condition of adhesive layer glass transition temperature, so that device layer can produce relative slippage with the rubber substrate.Heat treatment is generally annealing in process, can realize by heat treatment: (i) reduce the channel dimensions of device for the second time, improve performance of devices; (ii) interfacial stress that can abatement device-substrate and the compression of device improve the structural reliability of device.
(7) deposition organic semiconductor layer unit 10
(8) the additional flexibility base board unit 5, and this step is optional step, and base board unit 5 can be plastic base, flexible thin glass substrate and flexible Thin Stainless Steel plate base, are used for the distortion of the rear device of restriction shaping, keep the stable of size.
Fig. 4 is the technical process schematic diagram that the embodiment of the invention 2 is made the organic and inorganic thin-film transistors, and as we know from the figure, making of the present invention is organic-and the technical process of inorganic thin-film transistors is:
(1) the prepared substrate unit 4, and base board unit is the rubber substrate, can realize bending and stretching;
The rubber substrate that the flexible base, board selection has the higher elasticity deformability requires to surpass 50% elastic strain, still can restore to the original state after the release applied external force.
(2) stretch and surface treatment for base board unit, usually stretch more than 50%, the surface-coated adhesive;
At the adhesive layer of rubber substrate surface-coated one deck than the low glass state conversion temperature, to realize the bonding of substrate and functional layer.The glass transition temperature of requirement substrate and device function layer is higher than the glass transition temperature of adhesive layer.
(3) at substrate deposition grid 6;
(4) the organic dielectric layer of deposition unit 7;
(5) the drain electrode unit 12 of the source cell 11 of plated metal nanometer particle material and metal nano particle material;
The glass transition temperature of requirement device function layer is higher than the glass transition temperature of adhesive layer.
(6) carry out the heat treatment first time, temperature is a little more than the nanoparticle layers fusing point, be lower than the glass transition temperature of other structure sheaf, make the nano particle fusing form bulk metal, then source cell 11 and drain electrode unit 12 are converted into source cell 111 and drain electrode unit 121, and this moment, substrate kept extended state;
(7) the lax and heat treatment of substrate.Discharge the load that originally acted on the substrate, so that substrate can be in recovered part distortion under the free state;
Progressively discharge the elongation strain of rubber base board unit 4, so that substrate restores to the original state, so that relative slippage is arranged between device layer and the substrate, can effectively eliminate interface internal force, reduce channel dimensions;
Then adopt the Technology for Heating Processing the same with organic electronic device.
(8) deposition organic semiconductor layer unit 10;
(9) the additional flexibility base board unit 5, and this step is optional step, and base board unit 5 can be plastic base, flexible thin glass substrate and flexible Thin Stainless Steel plate base, are used for the distortion of the rear device of restriction shaping, keep the stable of size.
In above-described embodiment 1 and 2, the order of step (3) and step (5) and (6) also can be exchanged, i.e. first sedimentary origin pole unit 11 and drain electrode unit 12 on substrate, and after the heat treatment, deposit again organic dielectric layer unit 7 and deposit grid 6.
The whole device for preparing previously is attached to the attachment base unit, and attachment base can be plastic base, flexible thin glass substrate, flexible stainless steel foil substrate etc., can the retainer member physical dimension stable.According to requirements, this step is optional step.
Claims (9)
1. the preparation method of a thin film transistor of flexible electronic device comprises the steps:
(1) prepare substrate (4) flexible and that stretch, described substrate (4) is the rubber substrate;
(2) the described substrate (4) that stretches, and the substrate after stretching (4) surface-coated adhesive, the glass transition temperature of wherein said adhesive is lower than the glass transition temperature of described substrate (4);
(3) at described substrate (4) deposition grid (6);
(4) the device deposition organic dielectric layer unit (7) after processing through step (3);
(5) at described organic dielectric layer unit (7) difference sedimentary origin pole unit layer (11) and drain electrode elementary layer (12);
(6) at sedimentary origin pole unit layer (11) and the afterwards lax substrate of elementary layer (12) that drains, progressively discharge the elongation strain of rubber base board unit, so that the rubber base board unit restores to the original state, and heat-treat, eliminating the compression of interfacial stress and device, wherein said heat treatment temperature is controlled in the scope between rubber-based glass sheet attitude conversion temperature and the adhesive glass attitude conversion temperature;
(7) deposition organic semiconductor layer unit (10);
(8) device of step (7) being processed is attached on the attachment base unit (5), with the distortion of limiting device, keeps the stable of size;
By said process, namely finish the preparation of thin film transistor of flexible electronic device.
2. method according to claim 1, it is characterized in that, described deposition is all by directly being ejected into realization with corresponding function layer material solution, or by adopting soft etching technics, nano-imprint process, silk-screen printing technique or electric liquid fluid dynamic jet printing technique to realize.
3. method according to claim 2 is characterized in that, described functional layer material solution is polymer solution.
4. one of according to claim 1-3 described method is characterized in that described thin-film transistor is full OTFT.
5. method according to claim 1 is characterized in that, also comprises a process of thermal treatment between described step (5) and described step (6).
6. method according to claim 5 is characterized in that, the material solution of described source cell layer (11) and drain electrode elementary layer (12) is metal nanoparticle solution.
7. method according to claim 6 is characterized in that, described metal nanoparticle is argent nano particle or metallic copper nano particle.
8. one of according to claim 5-7 described method is characterized in that described thin-film transistor is the organic and inorganic thin-film transistor.
9. method according to claim 1 is characterized in that, described attachment base unit (5) can be plastic base, flexible thin glass substrate or flexible Thin Stainless Steel plate base.
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| CN106847862A (en) * | 2016-12-28 | 2017-06-13 | 深圳市华星光电技术有限公司 | A kind of flexible display substrate and preparation method thereof, flexible display preparation method |
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| CN102539379B (en) * | 2011-12-22 | 2014-01-08 | 复旦大学 | Optical fluid detection device based on inorganic oxide thin film and preparation method thereof |
| FR2997554B1 (en) * | 2012-10-31 | 2016-04-08 | Soitec Silicon On Insulator | METHOD OF MODIFYING AN INITIAL STRAIN STATUS FROM AN ACTIVE LAYER TO A FINAL STRAIN STATUS |
| CN105088142B (en) | 2015-07-30 | 2017-06-16 | 京东方科技集团股份有限公司 | A kind of evaporation coating method |
| KR102417115B1 (en) * | 2015-12-04 | 2022-07-06 | 삼성디스플레이 주식회사 | Flexible display apparatus |
| CN107204342B (en) * | 2016-03-16 | 2019-08-23 | 昆山工研院新型平板显示技术中心有限公司 | Flexible electronic device and its manufacturing method |
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| CN108898953B (en) * | 2018-07-04 | 2020-12-22 | 京东方科技集团股份有限公司 | Preparation method of flexible display panel, flexible display panel and display device |
| CN109166983A (en) * | 2018-09-05 | 2019-01-08 | 京东方科技集团股份有限公司 | The preparation method of inkjet printing methods and display base plate |
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| CN106847862A (en) * | 2016-12-28 | 2017-06-13 | 深圳市华星光电技术有限公司 | A kind of flexible display substrate and preparation method thereof, flexible display preparation method |
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