Metal oxide semiconductor ink and application method in a kind of inkjet printing technology
Technical field
The present invention relates to semiconductor materials and devices and inkjet printing technology, belongs to printed electronics field, specifically relates to
And metal oxide semiconductor ink and application method in a kind of inkjet printing technology.
Background technology
With the arrival of information age, Display Technique is just accelerating to large scale, and flexible, printable direction is developed, had
In the array driving display device of source, the thin-film transistor technologies of its core technology have attracted a large amount of enterprises and the attention of researcher.
Thin film transistor (TFT) is a kind of field-effect semiconductor device, including substrate, insulating layer, active layer, grid and source-drain electrode etc. are several
Important component.Wherein active layer has vital influence for device performance and preparation process.In the nearly more than ten years
In time, transistor active layer material is based on silicon materials, and TFT-LCD display devices are developed rapidly on this basis, and
Become mainstream display terminal.In recent years, metal oxide is due to its high grade of transparency and mobility and relatively low is prepared into
This and the characteristic prepared suitable for large area have attracted the exploitation and use of a large number of researchers and enterprise to the technology.However,
But current silica-base material and metal oxide semiconductor material is required for the film-forming process by sputtering, chemical deposition to prepare
Corresponding film is, it is necessary to which high vacuum environment and a large amount of mask plates, there is extremely complex technique and high cost of labor.
Present thin film transistor (TFT) mainstream technology is more more using being prepared on glass substrate by modes such as sputtering, chemical depositions
Crystal silicon or metal-oxide semiconductor (MOS), for mode of printing prepares transistor, this preparation method has higher
Manufacturing cost and complex technological process.It is right for mode of printing prepares inorganic, metal oxide thin film transistor (TFT)
There is higher compatibility in substrate selection, it is the most frequently used now, most hot without the advantages that mask plate inkjet printing to be become
A kind of preparation method of door.But the solution of inorganic, metal oxide material as marking ink when, its prepare MOTFT it is past
Toward having, electron mobility and on-off ratio be not high, the performance shortcomings such as performance degradation caused by film uniformity is bad and be unfavorable for reality
Border is applied and mass production.
The content of the invention
The object of the present invention is to provide the metal oxide semiconductor ink and application method in a kind of inkjet printing technology,
By realizing the blending of double solvents, metal oxide precursor and organic polymer in the solution before forming thin film, into
Organic polymer improves the uneven pattern of pattern after solvent volatilization during film, while have impact on presoma and be changed into gold
Belong to the process of oxide, the formation by promoting conducting channel improves the mobility of its electronics.
The present invention is realized using following methods:
A kind of metal oxide semiconductor ink in inkjet printing technology, the ink are molten with metal oxide semiconductor presoma
Solution based on liquid, completes to be blended and adulterates and be prepared into composite solution by adding the second solvent and organic polymer.It is described
Metal oxide semiconductor persursor material be made of the metallic salt of organic or inorganic, include acetylacetone,2,4-pentanedione radical ion, second
One or more anion in acid ion, nitrate ion, chlorion.The organic polymer is in the second solvent
Dissolubility is good, and with stable chemical property and does not have directly with the metal oxide semiconductor presoma in water oxygen and ink
The chemical reaction connect;
Second solvent includes esters and ketone.
The metal oxide semiconductor persursor material includes one kind in Indium Tris acetylacetonate and indium nitrate.
The molecular weight of the organic polymer is a certain molecular weight between 2000 to 1,000 ten thousand, including polystyrene and poly-
One kind in methyl methacrylate.
The good solvent of the metal oxide semiconductor presoma includes alcohols and ethers, has excellent mix with the second solvent
Dissolubility.
In the composite solution, the molar concentration of metal oxide semiconductor presoma between the M of 0.02 M ~ 0.8, and
The mass fraction ratio of organic polymer solute and metal oxide precursor solute is 0.1:100 to 5:Between 100.
The application method of metal oxide semiconductor ink:Composite solution is prepared smooth one by way of inkjet printing
On substrate, the contact angle of the substrate and composite solution is at 0 ~ 90 °, and the temperature of substrate is maintained at 30 ~ 50 DEG C during printing.This is compound
Solution is printed upon on substrate afterwards, it is necessary to by thermal anneal process, and annealing temperature is at 200 ~ 300 DEG C.
Compared with prior art, remarkable advantage of the invention and have the beneficial effect that:The metal oxide that the present invention makes is thin
Film transistor device, its active layer are prepared by the way of inkjet printing, its technique is simple, and operation is quick and precisely;And ink-jet is beaten
The used active layer of print is then the blending that metal oxide precursor and organic polymer are realized by using double solvents,
Organic polymer improves the uneven pattern of pattern after solvent volatilization during film forming, while have impact on presoma and be changed into
The process of metal oxide, the formation by promoting conducting channel improve the mobility of its electronics.
Brief description of the drawings
Fig. 1 is the structure diagram of metal oxide thin-film transistor device in the present invention.
Fig. 2 is the transfer characteristic curve figure and corresponding deposited picture that the embodiment of the present invention 1,2 is tested out.
Fig. 3 is the corresponding longitudinal sagittal height figure of the pattern prepared by this discovery embodiment 1,2.
The corresponding X-ray electronic energy spectrum of active layer film prepared by this discovery of Fig. 4 embodiment 1,2.
【Label declaration】Wherein 100 be p-type doped silicon wafer, and 110 be insulating layer, and 120 be active layer, and 130 be source-drain electrode.
Embodiment
The present invention will be described in further detail by specific embodiment below.
Embodiment 1
1) silicon chip with 100 nm thick silicon dioxide insulating layers is distinguished in acetone, isopropanol, chloroform, deionized water
Ultrasonic 10min, and dry up surface, vacuum drying using clean nitrogen.
2) silicon chip is subjected to oxygen plasma processing, specific method is:By the silicon chip insulating layer be placed in upwardly etc. from
In daughter cleaning machine cavity, plasma potential is set as 630 V, handles 5min, face up taking-up after being disposed.
3) metal-oxide semiconductor (MOS) presoma solute Indium Tris acetylacetonate is dissolved in 3ml's with 120 mg/ml of final concentration
Ethylene glycol monomethyl ether:Ethyl acetate (volume ratio 7:3) in double solvents, the polymethyl of 9mg is added on the basis of this solution
Sour methyl esters(Molecular weight 120000), 60 DEG C stirring 2h after be stored at room temperature it is overnight.The syringe filters mistake that the solution passes through 0.22um
Printed on after filter by type piezoelectric ink jet printer on demand on the insulating layer on silicon chip.The temperature of inkjet printing substrate is 40
DEG C, after the completion of printing, the silicon chip is in 80 °C of Heat preservation 30min, 225 °C of heating 1h afterwards.
4) the Au electrodes of 50 nm are formed on active layer using mask plate using the mode of physical vapour deposition (PVD).
Embodiment 2
1) silicon chip with 100 nm thick silicon dioxide insulating layers is divided in acetone, isopropanol, chloroform, deionized water
Not ultrasound 10min, and dry up surface, vacuum drying using clean nitrogen.
2) silicon chip is subjected to oxygen plasma processing, specific method is:By the silicon chip insulating layer be placed in upwardly etc. from
In daughter cleaning machine cavity, plasma potential is set as 630 V, handles 5min, face up taking-up after being disposed.
3) by metal-oxide semiconductor (MOS) presoma solute indium nitrate with the second for being dissolved in 3ml of 120 mg/ml of final concentration
Alcohol:Ethyl acetate (volume ratio 7:3) in double solvents, it is stored at room temperature after 60 DEG C of stirring 2h overnight.Add on the basis of this solution
Enter the polystyrene of 3mg(Molecular weight 200000), stirring at normal temperature 2h dissolvings are completely.The syringe filters that the solution passes through 0.22um
Printed on after filtering by type piezoelectric ink jet printer on demand on the insulating layer on silicon chip.The temperature of inkjet printing substrate is
40 °C, after the completion of printing, the silicon chip is in 80 °C of Heat preservation 30min, 225 °C of heating 1h afterwards.
4) the Au electrodes of 50 nm are formed on active layer using mask plate using the mode of physical vapour deposition (PVD).
Device architecture prepared by the present invention is as shown in Figure 1.Embodiment 1 and inorganic, metal oxide prepared by embodiment 2 are thin
The electricity transfer characteristic curve and corresponding deposited picture of film transistor are as shown in Fig. 2, the corresponding longitudinal direction of the pattern is cut at the same time
Face is highly as shown in Figure 3.As shown in Figure 2, inorganic, metal oxide thin film transistor (TFT) is after polystyrene is added, mobility from
4.2 cm2V-1s-113.7 cm are brought up to2V-1s-1, Fig. 4 illustrates that the chemical constituent of the film is changed, this is property
Can changed one of the main reasons.Meanwhile the uniformity of film is understood by Fig. 2 and Fig. 3, i.e. the whole height of film is poor,
There is larger lifting.After adding polystyrene in solution, low pattern is improved between the senior middle school of both sides, and " coffee ring " phenomenon obtains
To suppression.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.