阅读说明：本技术 一种溶液法制备金属氧化物tfd的方法 (A kind of method that solwution method prepares metal oxide TFD ) 是由 宁洪龙 梁志豪 姚日晖 周尚雄 梁宏富 张旭 张观广 蔡炜 朱镇南 彭俊彪 于 2019-07-15 设计创作，主要内容包括：本发明属于印刷电子技术领域,公开了一种溶液法制备金属氧化物TFD的方法。选取禁带宽度相近的金属氧化物绝缘材料和金属氧化物导电材料的前驱体,将其分别溶于同一种溶剂或互溶的溶剂得到绝缘材料前驱体溶液和导电材料前驱体溶液：然后将绝缘材料前驱体溶液和导电材料前驱体溶液依次旋涂于正极衬底上,热退火处理后沉积一层负电极材料,得到金属氧化物TFD。本发明基于溶液法旋涂禁带宽度相近且能溶于互溶或同一溶剂体系的绝缘层和导体层,利用绝缘层和导体层之间形成较大混溶区,使得金属氧化物薄膜器件表现出二极管的整流特性,制备出高性能的金属氧化物薄膜二极管。(The invention belongs to printed electronics fields, disclose a kind of method that solwution method prepares metal oxide TFD.Choose the presoma of metal oxide insulating materials and metal conductive oxide material similar in forbidden bandwidth, the solvent that it is dissolved in same solvent respectively or is dissolved each other obtains insulating materials precursor solution and conductive material precursor solution: and then insulating materials precursor solution and conductive material precursor solution are successively spun on positive substrate, one layer of negative electrode material is deposited after thermal anneal process, obtains metal oxide TFD.It is close the present invention is based on solwution method spin coating forbidden bandwidth and can be dissolved in and dissolving each other or the insulating layer and conductor layer of same dicyandiamide solution, using forming larger miscible area between insulating layer and conductor layer, so that metal-oxide film device shows the rectification characteristic of diode, high performance metal-oxide film diode is prepared.)

1. a kind of method that solwution method prepares metal oxide TFD, it is characterised in that including following preparation step:

(1) presoma for choosing metal oxide insulating materials and metal conductive oxide material similar in forbidden bandwidth, by it The solvent for being dissolved in same solvent respectively or dissolving each other obtains insulating materials precursor solution and conductive material precursor solution: described Metal oxide insulating materials similar in forbidden bandwidth is zirconium oxide, aluminium oxide, hafnium oxide or yttrium oxide, metal conductive oxide Material is indium oxide, stannous oxide or zinc oxide；

(2) one layer of positive electrode material is deposited in glass substrate surface, cleaning, drying obtains positive electrode；

(3) insulating materials precursor solution is spun on the positive electrode of step (2), then carries out thermal annealing, obtains metal oxygen Compound insulating layer of thin-film；

(4) conductive material precursor solution is spun on the metal oxide insulating layer film of step (3), then carries out heat and moves back Fire obtains conductor metal oxide layer film；

(5) one layer of negative electrode material is deposited on conductor metal oxide layer film surface, obtains metal oxide TFD.

2. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: the oxygen The presoma for changing zirconium is ZrOCl₂·8H₂O or Zr (NO₃)₄·5H₂O；The presoma of aluminium oxide is Al (NO₃)₃·9H₂O；Hafnium oxide Presoma be HfOCl₂·8H₂O；The presoma of yttrium oxide is Y (NO₃)₃·6H₂O。

3. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: the oxygen The presoma for changing indium is In (NO₃)₃·H₂O；The presoma of stannous oxide is Sn (NO₃)₂Or SnCl₂；The presoma of zinc oxide is Zn(NO₃)₂Or ZnCl₂。

4. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: described molten Agent is glycol monoethyl ether or ethylene glycol.

5. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: described exhausted The concentration of edge material precursor solution and conductive material precursor solution is not more than 0.6mol/L.

6. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: step (3) (4) number of spin coating described in is 1~5 time；The revolving speed of the spin coating is 4000~6000rpm, the time of spin coating each time For 30~40s, pre-anneal treatment is carried out after spin coating each time is complete, the temperature of pre-anneal treatment is 200~400 DEG C, the time is 3~ 5min。

7. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: step (3) (4) temperature of thermal annealing described in is 200~400 DEG C, and the time is 1~2h.

8. the method that a kind of solwution method according to claim 1 prepares metal oxide TFD, it is characterised in that: it is described just Electrode material is ITO, and the negative electrode material is Al electrode or Mo electrode.

9. a kind of metal oxide TFD, it is characterised in that: be prepared by method according to any one of claims 1 to 8.

Technical field

The invention belongs to printed electronics fields, and in particular to a kind of method that solwution method prepares metal oxide TFD.

Background technique

Thin film diode (Thin Film Diode, abbreviation TFD) is a kind of widely used semiconductor devices, most heavy The purposes wanted is that have high image quality, super low-power consumption, miniaturization, dynamic image for driving liquid crystal arrangement to change in the display Display capabilities and the characteristics of the quick reaction time.Existing mainstream thin film diode mostly uses silicon materials, however silicon materials have Transmitance it is low, it is with high costs the disadvantages of, and mostly use vacuum method to prepare thin-film semiconductor device now, there is cost of equipment height It is high, the disadvantages of operating process is complicated, and preparation condition is harsh.

Summary of the invention

In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of solution The method that method prepares metal oxide TFD.The present invention chooses metal oxide insulating materials and conduction material similar in forbidden bandwidth Material, and they are dissolved in solvent that is same or dissolving each other and obtains precursor solution, carry out spin coating then to prepare thin film diode (TFD), high performance metal-oxide film diode is successfully prepared.

Another object of the present invention is to provide a kind of metal oxide TFD being prepared by the above method.

The object of the invention is achieved through the following technical solutions:

A kind of method that solwution method prepares metal oxide TFD, including following preparation step:

(1) presoma of metal oxide insulating materials and metal conductive oxide material similar in forbidden bandwidth is chosen, The solvent that it is dissolved in same solvent respectively or is dissolved each other obtains insulating materials precursor solution and conductive material precursor solution: Metal oxide insulating materials similar in the forbidden bandwidth is zirconium oxide, aluminium oxide, hafnium oxide or yttrium oxide, metal oxide Conductive material is indium oxide, stannous oxide or zinc oxide；

(2) one layer of positive electrode material is deposited in glass substrate surface, cleaning, drying obtains positive electrode；

(3) insulating materials precursor solution is spun on the positive electrode of step (2), then carries out thermal annealing, obtains gold Belong to insulated by oxide layer film；

(4) conductive material precursor solution is spun on the metal oxide insulating layer film of step (3), is then carried out Thermal annealing obtains conductor metal oxide layer film；

(5) one layer of negative electrode material is deposited on conductor metal oxide layer film surface, obtains metal oxide TFD.

Preferably, the presoma of the zirconium oxide is ZrOCl₂·8H₂O (eight hydration zirconium oxychlorides) or Zr (NO₃)₄·5H₂O (five nitric hydrate zirconiums)；The presoma of aluminium oxide is Al (NO₃)₃·9H₂O (ANN aluminium nitrate nonahydrate)；The presoma of hafnium oxide is HfOCl₂·8H₂O (eight hydration oxychlorination hafniums)；The presoma of yttrium oxide is Y (NO₃)₃·6H₂O (six nitric hydrate yttriums).

Preferably, the presoma of the indium oxide is In (NO₃)₃·H₂O (indium nitrate hydrate)；The forerunner of stannous oxide Body is Sn (NO₃)₂(nitric acid stannous) or SnCl₂(stannous chloride)；The presoma of zinc oxide is Zn (NO₃)₂(zinc nitrate) or ZnCl₂ (zinc chloride).

Preferably, the solvent is glycol monoethyl ether or ethylene glycol.

Preferably, the concentration of the insulating materials precursor solution and conductive material precursor solution is not more than 0.6mol/ L。

Preferably, the number of spin coating described in step (3) and (4) is 1~5 time；The revolving speed of the spin coating be 4000~ 6000rpm, the time of spin coating each time are 30~40s, carry out pre-anneal treatment, the temperature of pre-anneal treatment after spin coating each time is complete Degree is 200~400 DEG C, and the time is 3~5min.

Preferably, the temperature of thermal annealing described in step (3) and (4) is 200~400 DEG C, and the time is 1~2h.

Preferably, the positive electrode material is ITO, and the negative electrode material is Al (aluminium) electrode or Mo (molybdenum) electrode.

A kind of metal oxide TFD, is prepared by the above method.

In the present invention, insulating materials and conductor material as similar in using forbidden bandwidth, and it is dissolved in the solvent that can be dissolved each other High performance thin film diode is made based on solwution method in system or same dicyandiamide solution.It the insulating layer of this thin film diode and leads Since forbidden bandwidth is close between body layer, while it being dissolved in the dicyandiamide solution that can be dissolved each other, therefore there are the miscible areas of larger thickness, and This miscible area can be used as insulating layer and conductor layer forms the transition region of conducting channel, when positive electrode applies positive voltage, due to folder The presence in miscellaneous area allows electronics to enter the conduction band of insulating layer of thin-film after conductor thin film from negative electrode, therefore forms electricity Stream.And when positive electrode applies negative voltage, since potential barrier is larger between grid and insulating layer conduction band, electronics can not transit to insulating layer Conduction band, therefore electric current is smaller, so that device be made to show the rectification characteristic as diode.Above-mentioned schematic illustration such as Fig. 1 institute Show (when wherein (a)-positive electrode applies positive voltage；(b) when-positive electrode applies negative voltage).And vacuum method prepares diode, insulation It is difficult to form the miscible area of such thickness between floor and conductor layer, and since thickness is too small, miscible area is difficult to play the role of transition, Even if electronics is also difficult to enter insulating layer by semiconductor layer when positive electrode applies forward voltage, therefore this is based on solwution method The superperformance being just achieved.

Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that

It is close the present invention is based on solwution method spin coating forbidden bandwidth and can be dissolved in dissolve each other or the insulating layer of same dicyandiamide solution and Conductor layer, using larger miscible area is formed between insulating layer and conductor layer, so that metal-oxide film device shows two poles The rectification characteristic of pipe prepares high performance metal-oxide film diode.

Detailed description of the invention

Fig. 1 is the schematic illustration of the metal oxide TFD of solwution method preparation of the present invention；

Fig. 2 is the structural schematic diagram of gained metal oxide TFD in the embodiment of the present invention；

Fig. 3 is the XPS figure of the insulating layer of thin-film of gained metal oxide TFD and thin film conductor layer in the embodiment of the present invention 1.

Specific embodiment

Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.