CN103000809A - Method for improving performance of organic field effect transistors - Google Patents
Method for improving performance of organic field effect transistors Download PDFInfo
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- CN103000809A CN103000809A CN2012105578837A CN201210557883A CN103000809A CN 103000809 A CN103000809 A CN 103000809A CN 2012105578837 A CN2012105578837 A CN 2012105578837A CN 201210557883 A CN201210557883 A CN 201210557883A CN 103000809 A CN103000809 A CN 103000809A
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Abstract
The invention provides a method for improving performance of field effect transistors based on organic semiconductor single crystal materials by utilizing oxidizing or reducing gas. By means of the method, gas adsorption processing is performed on the organic semiconductor single crystal materials according to types of semiconductors in the corresponding processing procedures of the field effect transistors which are of an air gap structure, a bottom grid electrode structure and a top grid electrode structure. The field effect transistor based on p-type organic semiconductor single crystal materials is exposed to the oxidizing gas to improve performance such as the migration rate, and the field effect transistor based on n-type organic semiconductor single crystal materials is exposed to the reducing gas to improve performance such as the migration rate. By means of the method, performance such as the migration rate and the switching ratio of the field effect transistors based on the organic semiconductor single crystal materials can be improved. Furthermore, the method is easy to operate, low in cost and wide in application prospect.
Description
Technical field
The invention belongs to organic microelectronics field, be specifically related to a kind of method that improves the field-effect transistor performance of organic single-crystal semi-conducting material
.
Background technology
After finding that first organic material has the field effect characteristic eighties in 19th century, (A.Tsumura, H. Koezuka, T. Ando, Appl. Phys. Lett. 1986,49,1210) field-effect transistor based on organic semiconducting materials is extensively concerned.Because its material source is wide, film technique is many, low temperature process, electrical properties easily modulate, can be with flexible substrate be compatible, device size is little, integrated level is high, be applicable to producing in enormous quantities and the outstanding advantage such as low-cost, organic field effect tube has boundless market prospects.It not only can make extensive complementary integrated circuit (B. Crone, A. Dodabalapur, Y.Y Lin, R. W. Filas, Z. Bao et al. Nature, 2000, 403, 521), broad area device, can also be for driving (the J.A. Rogers of flat-panel screens, Z. Bao, K. Baldwin, A. Dodabalapur, B. Crone et al. Proc. Nati. Acad. Sci. 2001, 98, 4835), smart card, the field such as identification card and gas sensor (B. Crone, A. Dodabalapur, A. Gelperin, L. Torsi, H.E. Katz, A. J. Lovinger, Z. Bao, Appl. Phys. Lett. 2001, 78, 2229).
Yet the performance of organic field effect tube still has a certain distance from the requirement of practical application.Therefore, current research mainly concentrates on and improves the device performance aspect.These performances mainly comprise: the mobility of device, threshold voltage, on-off ratio and sub-threshold slope etc.Wherein, mobility is one of the most important index of evaluation organic semiconducting materials and transistor device (G. Horowitz, Adv. Mater. 1998,10,365), and it determines whether certain organic semiconducting materials can practical application.Therefore, the mobility of raising organic semiconducting materials field-effect transistor is the major issue that is related to the organic field effect tube application prospect always.
At present, the mobility method of raising organic field effect tube device mainly contains following several: (1) designs and synthesizes has high performance novel organic semi-conductor material.The mobility of organic field effect tube and organic semi-conductor molecular configuration and crystal structure have close ties, especially the conjugation degree of molecule itself.Therefore, can obtain by designing and synthesizing the new material that mobility is higher.By researcher's continuous effort, constantly there is in recent years the novel organic semi-conductor material to be synthesized out (J.A. Merlo, C.R. Newman; C.P. Gerlach; T.W. Kelley, D.V.Muyres, S.E. Fritz; M.F. Toney; C.D. Frisbie, J. Am. Chem. Soc, 2005; 127,3997; A. Facchetti, M. Mushrush, M. Yoon, G.R. Hutchison, M.A. Ratner, T.J. Marks, J. AM. Chem. Sci. 2004,126,13859; Q. Miao, T. Nguyen, T. Someya, G.B. Blanchet, C. Nuckolls, J. AM. Chem. Sci. 2003,125,10284); (2) improvement and optimization organic field effect tube technology of preparing.As, to organic semiconductor raw material (the O.D Jurchescu that repeatedly purifies, J. Baas, T.T.M Palstra, Appl. Phys. Lett. 2004,84,3061), improve the degree of order and crystalline quality (Z. Bao, A.J. Lovinger, J. Brown, J. AM. Chem. Sci. 1998,120,207), insulating barrier (F. Garnier, G. Horowitz, the X.Z Peng of high-k, D. Fichou, Adv. Mater. 1990,2,592) etc. method improves the mobility of organic field effect tube; (3) adopt new field-effect transistor configuration to improve the performance (M. Morana, G. Bret, C. Brabec, Appl. Phys. Lett. 2005,87,153511) of organic field effect tube.
Although adopt above several method can improve the performance of organic field effect tube, have some problems.The one,, adopt these methods all can raise the cost and extend the R&D cycle.The 2nd,, these procedures complexity and shortage versatility.The 3rd,, these methods need to be constructed new device or exploitation new material, can not be for device or the material of existing device configuration or poor-performing.The problems referred to above have limited these techniques in the application that improves the organic field effect tube aspect of performance, in order to overcome these obstacles, promote the practical of organic assembly circuit, need the device optimization technique that development cost is cheap, technique is simple and applicability is strong.
Summary of the invention
The purpose of this invention is to provide a kind of simple, effective ways that adopt oxidizability or reducibility gas to improve the field-effect transistor performance based on the organic single-crystal semi-conducting material
.
Mainly comprise the steps:
1. for the air gap structure device:
1) prepare organic single-crystal semiconductor material.
2) prepare the air gap field-effect transistor with reference to Chinese invention patent (201210095207.2), overall configuration as shown in Figure 1.
3) after prepared by field-effect transistor, be filled with relevant gas (p-type semiconductor passes into the oxidizing gas such as nitrogen dioxide, nitric oxide, sulfur dioxide, and n-type semiconductor passes into the reducibility gas such as alcohol) in cavity, preserve certain hour.Arrive by gas absorption the performance that device is improved at the raceway groove place.
2. for bottom-gate structure organic single-crystal semiconductor device:
(1) prepare organic single-crystal semiconductor material;
(2) (p-type semiconductor passes into the oxidizing gas such as nitrogen dioxide, nitric oxide, sulfur dioxide synthetic organic single-crystal material to be put into to the gas of certain concentration, n-type semiconductor passes into the reducibility gas such as alcohol), make gas, at material surface, certain absorption be arranged.
(3) will have the organic single-crystal material of gas absorption, and utilize the way of mechanical transfer to be prepared into organic single-crystal field effect transistor.
(4) adopt the passivation layer packaging compatible with organic material such as PMMA.The device overall configuration as shown in Figure 2.
3. for the organic single-crystal semiconductor device of top grid structure:
(1) prepare the organic crystal material on specific substrate.
(2) before preparing insulating barrier, the machine crystalline material is put into to associated gas, and (p-type semiconductor passes into the oxidizing gas such as nitrogen dioxide, nitric oxide, sulfur dioxide, n-type semiconductor passes into the reducibility gas such as alcohol), make gas, at material surface, certain absorption be arranged.
(3) prepare insulating barrier and grid, complete the preparation of organic single-crystal field effect transistor.The device overall configuration as shown in Figure 3.
The method specifically has following advantage:
1) do not changing in device architecture and semi-conductive situation, device mobility is improved, cost is lower.
2) do not need comparatively complicated technological process, only need to add the gas absorption flow process in corresponding preparation link according to different device configurations, simple to operate.
3) due to the ubiquity of material gas absorption, device or material for existing configuration poor-performing, all can improve the performances such as mobility greatly by the gas absorption of corresponding types.There is very strong applicability.
The accompanying drawing explanation
Fig. 1 is for take the structural representation of the field-effect transistor that air gap is insulating barrier;
The structural representation that Fig. 2 is bottom-gate structure organic single-crystal semiconductor field effect transistor;
The structural representation that Fig. 3 is top grid structure organic single-crystal semiconductor field effect transistor;
Fig. 4 is for take the scanning electron microscope (SEM) photograph of the field-effect transistor that air gap is insulating barrier;
Fig. 5 is respectively the saturation region transfer curve of device in nitrogen and nitrogen dioxide;
Fig. 6 is respectively the saturation region transfer curve of device in nitrogen and nitric oxide;
Fig. 7 is respectively the saturation region transfer curve of device in nitrogen and sulfur dioxide;
Fig. 8 is respectively the saturation region transfer curve of device in air and alcohol;
Fig. 9 is the saturation region transfer curve of low gate device;
The saturation region transfer curve that Figure 10 is the top gate device;
In figure: 1. solid-state insulating barrier 8. passivation packaging insulating layers of dielectric substrate 2. grid 3. insulation support layer 4. organic single-crystal semi-conducting material 5. source-drain electrode 6. air gap insulating barrier 7. grid
Embodiment
With reference to Chinese invention patent (200510109070.1), the mode that adopts physical vapor to transport, prepare the micro/nano structure of CuPc, and the raw material CuPc used in deposition is bought from Alfa company, through 3 distillations, purifies.Preparation process is: raw material is placed in to the high-temperature region of two sections temperature control tube type resistance furnaces with vacuum system, collects substrate and be placed in low-temperature space, carry out physical vapor and transport deposition under the condition that passes into carrier gas (Ar).Can obtain the micro-/ nano linear structure of CuPc at low-temperature space.Device fabrication processes is with reference to Chinese invention patent (201210095207.2), and air gap trench adopts the PMMA that is spin-coated on substrate surface to prepare in conjunction with electron beam lithography.The source-drain electrode preparation, adopt gold plaque pad pasting electrode method or photoetching process to obtain.The micro-nano monocrystalline adopts the Mechanical Moving method to be placed on the top, air gap.
Concrete steps are as follows:
(1) cleaning glass substrate by the standard silicon chip cleaning, use subsequently the method for photoetching, preparation Ti/Au(10nm/20nm) electrode is as the grid of device;
(2) analyze pure petroleum ether solvent and be equipped with the PMMA that mass ratio is 6%, and the PMMA solution prepared is dripped on sheet glass, with the sol evenning machine spin coating, once (the spin coating time is 40s, rotating speed is 4500r/min), on the hot plate of 185 ℃, toast 90 seconds subsequently, solvent in PMMA is volatilized rapidly, finally can obtain the PMMA supporting layer of 200nm;
(3) preparing width by electron beam lithography on grid is the smooth grooves in 3.3 microns bottoms (electric conducting material, i.e. grid), and channel bottom is Ti/Au, i.e. grid.The groove both sides are for supporting the CuPc nanobelt.
(4) mode of micro-nano crystal by adopting Mechanical Moving is placed on the top, air gap to single CuPc nanobelt, and micro-nano monocrystalline width is 300nm.
(5) adopt gold plaque pad pasting electrode method (Tang et al. Appl. Phys. Lett. 92,083309,2008) to prepare source-drain electrode, and CuPc is connected with macroscopical electrode simultaneously.
(6) semiconductor and channel bottom form the gate insulator of device to the air gap between grid, the height that the thickness of PMMA supporting layer is the air gap insulating barrier, and the distance between two electrodes is groove width.The channel width of the single fieldtron of micro-nano monocrystalline of finally constructing is 300nm, and channel length is 3.3 μ m.Fig. 1 and Fig. 4 are divided into structural representation and the SEM photo of the field effect gas sensor that grid prepared by the single nanobelt of CuPc is Ti/Au.
(7) device of putting up and be connected in macroscopical electrode is connected on chip by the gold wire bonder connection technology, and is installed in the homemade stainless steel test macro in laboratory.
(8) pass into the nitrogen of 99.999% purity of 500sccm in cavity, more than 30 min, until device reaches stable fully.
(9) device stable after, then be filled with in cavity and pass into nitrogen dioxide.While testing the saturation region transfer curve, source-drain current is-15 V, and the gated sweep scope is that 10V is between-10 V.
(10) by the transfer curve of semiconductor coefficient measuring instrument (Keithley 4200-SCS) difference measuring element in nitrogen and nitrogen dioxide, as shown in Figure 5.By calculating, the mobility of device is by 0.03 initial cm
2/ V.s brings up to 0.37 cm
2/ V.s.
(1) adopt step (1)-(8) in implementation column 1 to obtain field-effect transistor.
(2) after field-effect transistor is stablized, pass into nitric oxide.By two mass flowmenter mixing High Purity Nitrogens and standard nitric oxide, regulate.Accurately control the total flow of 500sccm by mass flowmenter.While testing the saturation region transfer curve, source-drain current is-15 V, and the gated sweep scope is that 10V is between-10 V.
(3) by the transfer curve of semiconductor coefficient measuring instrument (Keithley 4200-SCS) difference measuring element in nitrogen and nitric oxide, as shown in Figure 6.By calculating, the 0.001cm that the mobility of device is initial
2/ V.s brings up to 0.006cm
2/ V.s.
(1) adopt step (1)-(8) in implementation column 1 to obtain device.
(2) after device is stablized, pass into sulfur dioxide.By two mass flowmenter mixing High Purity Nitrogens and standard sulfur dioxide, regulate.Accurately control the total flow of 500sccm by mass flowmenter.While testing the saturation region transfer curve, source-drain current is-15 V, and the gated sweep scope is that 10V is between-10 V.
(3) by the transfer curve of semiconductor coefficient measuring instrument (Keithley 4200-SCS) difference measuring element in nitrogen and sulfur dioxide, as shown in Figure 7.By calculating, the 0.007cm that the mobility of device is initial
2/ V.s brings up to 0.047cm
2/ V.s.
(1) adopt step (1)-(8) in implementation column 1 to obtain device.Difference is: p-type CuPc is substituted with n-type perfluor CuPc.
(2) after device is stablized, the alcohol of one glass of 10ml is put into to cavity, tested.During test saturation region transfer curve, source-drain current is-40 V, the gated sweep scope is-5V to 40 V between.
(3) by the transfer curve of semiconductor coefficient measuring instrument (Keithley 4200-SCS) difference measuring element in nitrogen and alcohol, as shown in Figure 8.By calculating, the 0.0038cm that the mobility of device is initial
2/ V.s brings up to 0.0043cm
2/ V.s.
(1) adopt the method in implementation column 1 to prepare CuPc monocrystalline micro-/ nano line.
(2) synthetic CuPc monocrystalline micro-/ nano line is put into to the gas nitrogen dioxide of certain concentration, made gas, at material surface, certain absorption be arranged.
(3) will have the organic single-crystal material of gas absorption, and utilize the way of mechanical transfer to be prepared into the field-effect transistor of bottom-gate structure.Structure is for as shown in Figure 2.
(4) adopt the PMMA passivation layer packaging for method of spin coating.
(5) by semiconductor coefficient measuring instrument (Keithley 4200-SCS) measuring element transfer curve, as shown in Figure 9.While testing the saturation region transfer curve, source-drain current is-15 V, and the gated sweep scope is that 10V is between-15 V.
By calculating, the mobility of device is 0.5cm
2/ V.s.
(1) adopt the method in implementation column 1 to prepare CuPc monocrystalline micro-/ nano line.
(2) utilize the way of mechanical transfer that CuPc monocrystalline micro-/ nano line is moved on to Si/SiO
2on substrate.
(3) adopt gold plaque pad pasting electrode method (Tang et al. Appl. Phys. Lett. 92,083309,2008) to prepare source-drain electrode.
(3) before preparing insulating barrier, device is put into to the gas nitric oxide of certain concentration, make gas, at material surface, certain absorption be arranged.
(4) the PMMA insulating barrier of step 2 spin coating 200 nm in implementation column 1.
(5) adopt gold plaque pad pasting electrode method (Tang et al. Appl. Phys. Lett. 92,083309,2008) to prepare grid.Device architecture is shown in Fig. 3.
(6) by semiconductor coefficient measuring instrument (Keithley 4200-SCS) measuring element transfer curve, as shown in figure 10.During test saturation region transfer curve, source-drain current be-15 V, the gated sweep scope be 10V extremely-15V between.
By calculating, the mobility of device is 0.2cm
2/ V.s.
Claims (3)
1. improve the method for field-effect transistor performance of the organic single-crystal semi-conducting material of air gap structure,
Prepare organic single-crystal semiconductor material and air gap field-effect transistor with reference to prior art, it is characterized in that: after prepared by field-effect transistor, be filled with relevant gas in cavity, wherein: p-type semiconductor passes into oxidizing gas, be nitrogen dioxide or nitric oxide or sulfur dioxide, n-type semiconductor passes into the reproducibility alcohol gas, makes gas absorption arrive the raceway groove place.
2. improve the method for field-effect transistor performance of the organic single-crystal semi-conducting material of bottom-gate structure, prepare organic single-crystal semiconductor material with reference to prior art, it is characterized in that: synthetic organic single-crystal material is put into to relevant gas wherein: p-type semiconductor passes into oxidizing gas, be nitrogen dioxide or nitric oxide or sulfur dioxide, n-type semiconductor passes into reducibility gas alcohol, makes gas, at material surface, certain absorption be arranged; Organic single-crystal material by existing gas absorption, utilize the way of mechanical transfer to be prepared into organic single-crystal field effect transistor; Adopt the PMMA passivation layer packaging compatible with organic material.
3. improve the method for field-effect transistor performance of the organic single-crystal semi-conducting material of top grid structure, prepare the organic crystal material on specific substrate with reference to prior art, it is characterized in that: before preparing insulating barrier, the organic crystal material is put into to relevant gas, wherein: p-type semiconductor passes into oxidizing gas, be nitrogen dioxide or nitric oxide or sulfur dioxide, n-type semiconductor passes into the reproducibility alcohol gas, makes gas, at material surface, certain absorption be arranged; Prepare insulating barrier and grid, complete the field-effect transistor preparation.
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| WO2016008277A1 (en) * | 2014-07-17 | 2016-01-21 | 东北师范大学 | Organic single crystal field effect circuit and preparation method therefor |
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| CN104713930B (en) * | 2015-03-17 | 2017-07-21 | 东北师范大学 | A kind of method of the identification gaseous species based on field-effect gas sensor |
| CN104713930A (en) * | 2015-03-17 | 2015-06-17 | 东北师范大学 | Gas type identifying method based on field effect gas sensor |
| KR101792644B1 (en) * | 2017-03-02 | 2017-11-02 | 울산과학기술원 | High-mobility transistor and a method of manufacturing the same |
| CN107340315A (en) * | 2017-05-18 | 2017-11-10 | 新疆工程学院 | A kind of FET formula gas sensors with composite insulation structure and preparation method thereof |
| CN108931322A (en) * | 2017-05-24 | 2018-12-04 | 东北师范大学 | A kind of hypersensitive field effect type touch sensor and its application in terms of micro-dimension object detection |
| KR101824686B1 (en) | 2017-08-10 | 2018-02-01 | 울산과학기술원 | High-mobility transistor |
| CN108956707A (en) * | 2018-04-27 | 2018-12-07 | 苏州诺登德智能科技有限公司 | A kind of NO2The preparation method of sensor |
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