CN108155297A - A kind of method that graphene top electrode is prepared using laminating method - Google Patents
A kind of method that graphene top electrode is prepared using laminating method Download PDFInfo
- Publication number
- CN108155297A CN108155297A CN201611100965.3A CN201611100965A CN108155297A CN 108155297 A CN108155297 A CN 108155297A CN 201611100965 A CN201611100965 A CN 201611100965A CN 108155297 A CN108155297 A CN 108155297A
- Authority
- CN
- China
- Prior art keywords
- graphene
- silicone polymer
- dimethyl silicone
- pdms
- top electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Abstract
The invention discloses a kind of methods that graphene top electrode is prepared using laminating method, first with wet method or dry method transfer method, transfer graphene on PDMS；Then graphene is pressed onto together with PDMS layer on the organic function layer of semiconductor devices, the graphene on PDMS is tightly adhered on organic function layer by Van der Waals for, the top electrode as device.The present invention prepares the organic light emitting diode of all-transparent or other semiconductor devices using graphene as top electrode by contact laminating graphene top electrode, simple and convenient, of low cost.
Description
Technical field
The present invention relates to the electrode fabrication fields of semiconductor devices, and in particular to a kind of to have been prepared using laminating method
The method of the graphene top electrode of the devices such as machine light emitting diode.
Background technology
The top electrode of Organic Light Emitting Diode is more to be prepared using the method for vacuum evaporation or sputtering, and it is mostly opaque or
Semi-transparent metals electrode or tin indium oxide (ITO) electrode.Metal electrode and ITO electrode electric conductivity are relatively good, but there is also more
Problem：Using high vacuum vapor deposition or sputtering, time-consuming longer, cost is higher；Metal electrode flexibility and tensile strength ratio are relatively low；It is cloudy
The low workfunction metal that pole uses is oxidized easily；Metallic element in metal electrode can be in device operation to organic layer
Middle diffusion, causes device to be quenched；For ITO electrode, contain the more rare thulium of raw material.Therefore, being badly in need of will
It finds a kind of chemical property to stablize, abundant raw materials, the transparency is good, and flexibility is good and the replacement electrode material of good conductivity.
In recent years, many researchs are expanded around transparent flexible electrode, including carbon nanotube, metal nanometer line, Yi Jijin
Category-semiconducting compound and graphene etc. instead of ITO are graphenes wherein most potential.Graphene is one layer of sp2 hydridization
Single layer of carbon atom layer, good conductivity, mobility is high, and transparency is high, can be carried out by chemically or physically method controllable doped
Adjust work function and square resistance, raw material are relatively abundanter, chemical property is more stable, ultra-thin, and flexibility is good, tensile strength
Height, current-carrying capacity is big, and in organic light emitting diode, the application report in terms of the electrode of optical detector and solar cell has
Very much.For organic light emitting diode, mostly using graphene as hearth electrode, a several pieces are used as top electrode for research.By stone
Black alkene had not only been used as top electrode but also the report as hearth electrode only has one, this report is to shift graphene using dry method, was turning
The graphene of shifting is inserted into gold nano grain or nano silver wire to reduce the square resistance of graphene and adjust graphite between layers
The work function of alkene, this method technics comparing is complicated, need to not be graphene conductive merely by metal.Therefore, it is necessary to solve with
The upper problem preferably using the electrode advantage of graphene, is applied in device, and avoid the ginseng of metal as possible
With simplifying preparation process, reducing cost, can have the Practical significance of bigger in this way.
Invention content
The purpose of the present invention is to provide a kind of simple and convenient, low-cost graphene top electricity for preparing semiconductor devices
The method of pole, by contact laminating graphene top electrode come prepare the organic light emitting diode of all-transparent or other using graphene as
The semiconductor devices of top electrode.
Technical scheme is as follows：
A kind of method for preparing semiconductor devices graphene top electrode, includes the following steps：
1) it using wet method or dry method transfer method, transfers graphene on dimethyl silicone polymer (PDMS)；
2) graphene transferred on PDMS is pressed onto together with PDMS layer on the organic function layer of semiconductor devices, on PDMS
Graphene electrodes be tightly adhered on organic function layer by Van der Waals for so that device can be connected.
Above-mentioned steps 1) the graphene number of plies as needed determines the number of transfer, transfer two is needed under normal circumstances
It is secondary, it could preferably cover substrate.The number of plies of graphene is that the number of plies for the graphene for being multiplied by growth by the number that shifts determines
, if necessary to than relatively low square resistance, shift repeatedly.
Above-mentioned steps 1) in, preferably transfer graphene to the polyethylene terephthalate of surface spin coating PDMS
(PET) on substrate or on PDMS substrates, then the surface spin coating glass of PDMS or other transparent substrates on.Spin coating
Rotating speed when PDMS thickness is by adjusting the ratio and spin coating of A glue and B glue in PDMS determines, preferably 0.1mm.Turning
It moves before graphene, with air plasma processing PDMS surfaces, to improve the hydrophily on PDMS surfaces, the time of processing is preferred
For 40s to 1min.
In one embodiment of the invention, step 1) grows graphite by chemical vapour deposition technique (CVD) on copper foil
Then alkene carries out wet method transfer：The first graphene surface spin coating polymethyl methacrylate (PMMA) on copper foil is grown on, then
This copper foil is immersed in ferric chloride solution is completely dissolved copper foil, is then successively transferred to the graphene being attached on PMMA dilute
In hydrochloric acid and water, finally graphene is picked up with the transparent substrates of PDMS substrates or spin coating PDMS, soaked in acetone soln later
1 hour removal PMMA coating of bubble, is then cleaned with ethanol solution and deionized water, is dried up with nitrogen gun.
Above-mentioned steps 2) lamination process is to be carried out in nitrogen glove box at room temperature.Graphene top electrode on PDMS is put down
When being put on organic function layer, it can cause two without the Van der Waals for applied between other external force, with organic function layer
Person combines from one side, air is slowly discharged, until the two is closely linked.If occurring uneven situation sometimes, have
Some places can not combine, can be slightly with forcing on side.
The light emitting diode with graphene top electrode can be prepared using the above method, is revolved successively on hearth electrode first
Transmission layer material and emitting layer material etc. are applied, then forces up the PDMS graphene layers shifted as top electrode.Light-emitting diodes
The hearth electrode material of pipe can be ITO or the graphene shifted with PET, glass or other transparent substrates.
PDMS is a kind of material with elasticity and adhesion strength, it can make graphene with contact by Van der Waals for
The organic function layer of semiconductor devices be tightly adhered to each other, can be in electrical contact well.By transferring graphene to
On PDMS, and processing is optimized to PDMS substrates, all-transparent graphene top electrode can be obtained.
In addition to Organic Light Emitting Diode, the devices such as liquid crystal cell, graphene photovoltaic cell and graphene capacitance are being made
In the process, graphene top electrode can also be prepared, and realize good electrical contact with this method.
Description of the drawings
The graphene being transferred in Fig. 1 embodiments 1 on various substrates (PET substrate, PDMS substrates and PDMS/PET substrates)
Square resistance with the variation diagram of the graphene number of plies.
Fig. 2 embodiments 2 do bottom cathode using ITO, and the quantum dot that cathode is made of the PDMS/PET graphenes shifted is organic
The luminous picture of inorganic hybridization electroluminescent diode.
PDMS/PET, Graphene/PDMS/PET, ITO/ glass and using graphene as top electrode in Fig. 3 embodiments 2
Quantum dot light emitting device transmitance with wavelength change curve.
Fig. 4 embodiments 2 do bottom cathode using ITO, and the quantum dot that top anode is made of the PDMS/PET graphenes shifted is organic
Inorganic hybridization electroluminescent diode and the comparative device to make top electrode with the graphene of evaporating Al replacement PDMS/PET transfers
Light-emitting data figure.
Specific embodiment
With reference to two embodiments, the invention will be further described, the model of but do not limit the invention in any way
It encloses.
Embodiment 1：
The preparation of PDMS substrates and PDMS/PET substrates.
The preparation process of PDMS substrates is：The A glue of PDMS will be prepared with B glue by 1:7 volume ratio is equipped with, and is stirred 5 minutes,
Stand half an hour discharge bubble；It pours into later on the silicon chip of polishing, after placing a night, is placed on Baking out on 100 DEG C of hot plate
10 minutes；PDMS is removed from silicon chip, it is about 1~2mm to obtain thickness, and length and width are the PDMS transparent bodies of 1.5cm, with contact
The side of silicon chip shifts and air plasma is used to clean PDMS tables in the case where vacuum degree is less than 300Pa before to shift graphene
Face 40 seconds.
The preparation process of PDMS/PET substrates is：PET acetone, second alcohol and water are cleaned up；The A glue of PDMS will be prepared
1 is pressed with B glue:7 volume ratio is equipped with, and is stirred 5 minutes, stands half an hour discharge bubble；PDMS is revolved on Tu to PET later, is turned
Speed is 2000rpm, time 30s；Then it is placed on 100 DEG C of hot plate and heats 10 minutes；It is about 0.14mm (its to obtain overall thickness
Middle PDMS thickness 0.1mm), length and width are the PDMS/PET transparent substrates of 2cm, shift graphene with the PDMS sides, shift it
It is preceding to clean PDMS surfaces 40 seconds in the case where vacuum degree is less than 300Pa with air plasma.
Respectively with PET substrate, PDMS substrates and PDMS/PET substrates transfer graphene.Specific experiment step is：Use wet method
Transfer is grown in the graphene on copper foil with chemical vapour deposition technique, the first spin coating PMMA on graphene, then will adhere to this graphite
The copper foil of alkene is immersed in ferric chloride solution (0.10g/mL), treats that copper foil is completely dissolved, then the stone that will be attached on PMMA successively
Black alkene is transferred to dilute hydrochloric acid (hydrochloric acid: water=1:2, volume ratio) and water in, finally pick up graphene with substrate, later acetone,
It is impregnated in ethanol solution to remove PMMA coatings, the substrate selected here is respectively PET substrate, PDMS substrates and PDMS/
PET substrate.The graphene that we grow is double-deck, since the square resistance of graphene that transfer once obtains is bigger, institute
Above step to be repeated as many times, the number of plies of obtained graphene is that the number of transfer is multiplied by the number of plies of graphene.
It is served as a contrast using be transferred to PET substrate, PDMS substrates and the PDMS/PET that Hall Measurement System (Hall HL5500) measures
The square resistance of graphene on bottom, they are as shown in Figure 1 with the changing rule of the number of plies of graphene.
From fig. 1, it can be seen that with increase graphene the number of plies, PET substrate transfer graphene square resistance by 930 Ω/
(2 layers) drops to 570 Ω/ (4 layers), and the square resistance of the graphene of PDMS substrates transfer is dropped to by 7170 Ω/ (4 layers)
1660 Ω/ (6 layers), the square resistance of the graphene of PDMS/PET substrates transfer drop to 540 Ω/ by 710 Ω/ (4 layers)
(6 layers), then to 430 Ω/ (8 layers).It can be seen that the square resistance of the graphene of PDMS/PET transfers was shifted than PDMS
It is small.
Embodiment 2：
Make top electrode using the PDMS/PET graphenes shifted, make hearth electrode with ITO, the all-transparent quantum dot of preparation is organic
Inorganic hybridization electroluminescent diode.
Specific experiment step is：On the cathode of ITO bottoms, Tu Zinc oxide nanoparticle is revolved successively as electron transfer layer,
CdSSe/ZnS quantum dots are as luminescent layer；It is transferred to and is evaporated in vacuo in chamber later, 1,1-Bis [(di-4- are deposited
Tolylamino) phenyl]-Cyclohexane (TAPC) hole transmission layers and MoO3Hole injection layer；Then by sample
It is transferred in nitrogen glove box, at room temperature, 6 layer graphenes shifted on PDMS/PET is laminated to MoO3On layer.In order to do
Reference, we are also prepared for being made with the graphene of evaporating Al replacement PDMS/PET transfers the comparative device of top electrode.
Device is obtained using ultraviolet-uisible spectrophotometer (PR705) measurement combined with 2400 digital sourcemeters of Keithley
The current-voltage-light characteristic of part.The luminous picture of device is shown in Fig. 2, and the transmitance data of device are shown in Fig. 3, the electroluminescent hair of device
The experimental data of light characteristic is shown in Fig. 4.
Figure it is seen that device shines uniformly.From figure 3, it can be seen that the transmitance of device is in 500~850nm ranges
It is inside 70%~80%.From fig. 4, it can be seen that the light emitting diode with quantum dots using graphene as top electrode prepared by the method is opened
Voltage is opened in 4V or so, maximum current efficiency and power efficiency are about 0.32cd/A and 0.19lm/W respectively, than using Al as
The current efficiency and power efficiency of the comparative device of top electrode are somewhat larger.Due to the square resistance (~500 of graphene top electrode
Ω/) than Al square resistance (<1 Ω/) it is much larger, so the light emission luminance for the quantum dot light emitting device that the former is formed is most
Greatly~30cd/m2, than the maximum luminousing brightness (~1000cd/m for the device that the latter is formed2) small.
But, the top metal electrode generally used that Al is represented, electrode that is generally opaque, and easily aoxidizing, and stone
Black alkene electrode transparency is higher, and chemical property is more stable, and mechanical strength is higher, has very in flexible and transparent device
Big advantage.Moreover, now with the method that many reports effectively chemically or physically adulterate, graphene top electrode can be improved
Square resistance and work function by using these methods, may be such that the light emitting diode with quantum dots that graphene is top electrode
Light emission luminance catch up with even more than traditional device using metal as top electrode.
Claims (9)
1. a kind of method for preparing semiconductor devices graphene top electrode, includes the following steps：
1) it using wet method or dry method transfer method, transfers graphene on dimethyl silicone polymer；
2) graphene transferred on dimethyl silicone polymer is laminated to having for semiconductor devices together with dimethyl silicone polymer
In machine functional layer, the graphene on dimethyl silicone polymer is tightly adhered on organic function layer by Van der Waals for, is made
Top electrode for device.
2. the method as described in claim 1, which is characterized in that the step 1) is repeatedly shifted, and makes to be transferred to poly- diformazan
Graphene on radical siloxane reaches the number of plies of needs.
3. the method as described in claim 1, which is characterized in that dimethyl silicone polymer lining is transferred graphene in step 1)
In on the bottom or surface spin coating transparent substrates of dimethyl silicone polymer.
4. method as claimed in claim 3, which is characterized in that the dimethyl silicone polymer thickness of spin coating is 0.1mm.
5. the method as described in claim 1, which is characterized in that step 1) uses air plasma before graphene is shifted
Handle dimethyl silicone polymer surface.
6. the method as described in claim 1, which is characterized in that step 1) grows stone by chemical vapour deposition technique on copper foil
Then black alkene carries out wet method transfer：The first graphene surface spin coating polyethylene terephthalate on copper foil is grown on, then
Being immersed in ferric chloride solution is completely dissolved copper foil, the stone that then will be attached on polyethylene terephthalate successively
Black alkene is transferred in dilute hydrochloric acid and water, finally with dimethyl silicone polymer substrate or the spin coating transparent lining of dimethyl silicone polymer
Bottom picks up graphene, is impregnated in acetone soln remove polyethylene terephthalate coating later, then use ethanol solution
It is cleaned with deionized water solution, is dried up with nitrogen gun.
7. the method as described in claim 1, which is characterized in that step 2) carries out being laminated in nitrogen glove box at room temperature
Journey.
8. the method as described in claim 1, which is characterized in that semiconductor devices described in step 2) is for light emitting diode or too
Positive energy battery.
9. the method as described in claim 1, which is characterized in that the hearth electrode material of the light emitting diode is tin indium oxide,
The graphene either shifted with transparent substrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611100965.3A CN108155297A (en) | 2016-12-05 | 2016-12-05 | A kind of method that graphene top electrode is prepared using laminating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611100965.3A CN108155297A (en) | 2016-12-05 | 2016-12-05 | A kind of method that graphene top electrode is prepared using laminating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108155297A true CN108155297A (en) | 2018-06-12 |
Family
ID=62470747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611100965.3A Pending CN108155297A (en) | 2016-12-05 | 2016-12-05 | A kind of method that graphene top electrode is prepared using laminating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108155297A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832015A (en) * | 2018-06-25 | 2018-11-16 | 上海大学 | A kind of OLED device and preparation method thereof |
| CN108832020A (en) * | 2018-06-25 | 2018-11-16 | 上海大学 | A kind of flexible substrate composite construction and the preparation method and application thereof |
| CN111446378A (en) * | 2019-01-17 | 2020-07-24 | 中国科学院金属研究所 | Method for manufacturing transparent organic light-emitting diode |
| CN112086580A (en) * | 2020-09-15 | 2020-12-15 | 武汉华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN112885980A (en) * | 2021-01-29 | 2021-06-01 | 南京大学 | Method for manufacturing graphene all-electrode transparent OLED device |
| CN114899249A (en) * | 2022-03-17 | 2022-08-12 | 西北工业大学 | Self-driven photoelectric detector based on tungsten diselenide and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104091892A (en) * | 2014-06-13 | 2014-10-08 | 重庆绿色智能技术研究院 | Organic semiconductor photoelectric device based on graphene electrode |
| US20150060768A1 (en) * | 2013-08-13 | 2015-03-05 | The Board Of Regents Of The University Of Texas System | Method to improve performance characteristics of transistors comprising graphene and other two-dimensional materials |
| CN105621401A (en) * | 2015-12-28 | 2016-06-01 | 中国科学院重庆绿色智能技术研究院 | Multi-layer stacking and transferring method for graphene |
-
2016
- 2016-12-05 CN CN201611100965.3A patent/CN108155297A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150060768A1 (en) * | 2013-08-13 | 2015-03-05 | The Board Of Regents Of The University Of Texas System | Method to improve performance characteristics of transistors comprising graphene and other two-dimensional materials |
| CN104091892A (en) * | 2014-06-13 | 2014-10-08 | 重庆绿色智能技术研究院 | Organic semiconductor photoelectric device based on graphene electrode |
| CN105621401A (en) * | 2015-12-28 | 2016-06-01 | 中国科学院重庆绿色智能技术研究院 | Multi-layer stacking and transferring method for graphene |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832015A (en) * | 2018-06-25 | 2018-11-16 | 上海大学 | A kind of OLED device and preparation method thereof |
| CN108832020A (en) * | 2018-06-25 | 2018-11-16 | 上海大学 | A kind of flexible substrate composite construction and the preparation method and application thereof |
| CN111446378A (en) * | 2019-01-17 | 2020-07-24 | 中国科学院金属研究所 | Method for manufacturing transparent organic light-emitting diode |
| CN112086580A (en) * | 2020-09-15 | 2020-12-15 | 武汉华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN112885980A (en) * | 2021-01-29 | 2021-06-01 | 南京大学 | Method for manufacturing graphene all-electrode transparent OLED device |
| CN114899249A (en) * | 2022-03-17 | 2022-08-12 | 西北工业大学 | Self-driven photoelectric detector based on tungsten diselenide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108155297A (en) | A kind of method that graphene top electrode is prepared using laminating method | |
| CN102709310B (en) | A kind of flexible organic light-emitting transistor display device | |
| Kim et al. | Paper as a substrate for inorganic powder electroluminescence devices | |
| CN107610802B (en) | Transparent conductive film, photoelectric device and preparation method thereof | |
| Han et al. | Flexible transparent electrodes for organic light-emitting diodes | |
| CN102610725B (en) | Semiconductor quantum dot light-emitting diode and preparing method thereof | |
| CN103972416B (en) | Semiconductor quantum dot LED based on reverse structure and preparation method thereof | |
| TWI503050B (en) | An electrically conducting structure for a light transmissible device | |
| CN109980109B (en) | QLED device and preparation method thereof | |
| CN104054191A (en) | Organic light-emitting device and method for processing an organic light-emitting device | |
| CN105453292A (en) | Substrate for photoelectric device and photoelectric device comprising same | |
| CN103427029A (en) | Flexible organic luminescent device and preparation method thereof | |
| WO2009106583A1 (en) | Electroluminescent device | |
| WO2014015284A1 (en) | High efficiency organic light emitting devices | |
| CN106784202A (en) | QLED devices and preparation method thereof | |
| CN102244204B (en) | OLED device and preparation method thereof | |
| CN108461590A (en) | A kind of light emitting diode with quantum dots device and preparation method thereof | |
| KR20120001684A (en) | Transparent conducting film, preparing method for the same, and transparent electrode and devices using the same | |
| Das et al. | Influence of Ga-doped transparent conducting ZnO thin film for efficiency enhancement in organic light-emitting diode applications | |
| CN111816794A (en) | PEIE (Positive electrode interference) intervention standard inverted QLED (quantum dot light emitting diode) device and preparation method thereof | |
| CN106098957B (en) | A kind of QLED and preparation method thereof | |
| US11708499B2 (en) | Method of manufacturing highly conductive polymer thin film including plurality of conductive treatments | |
| Wang et al. | Small-molecular organic solar cells with C60/Al composite anode | |
| CN102509756A (en) | Novel total inorganic oxide quantum dot LED based on FTO, and manufacturing method thereof | |
| CN102542926B (en) | Organic photovoltaic and electroluminescent combined display device and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180612 |