Patent Application
20080315190
The present invention relates to an organic thin film transistor and a method for surface modification of a gate insulating layer in the organic thin film transistor.
Generally, there is known an organic thin film transistor using an organic substance as a material, and such an organic thin film transistor uses an oxide, for example, as a gate insulating layer.
Then, in the organic thin film transistor using an oxide as the gate insulating layer, various methods of performing surface modification of the gate insulating layer formed of an oxide have been proposed to improve its transistor characteristics.
Conventionally, as a method of performing surface modification of the gate insulating layer formed of the oxide, a method of forming a self-assembled film such as octadecyltrichlorosilane (OTS) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS), for example, has been mentioned. Meanwhile, refer to Non-patent Documents 1 to 4 for the method concerning OTS, and refer to Non-patent Document 5 for the method concerning HMDS.
However, the above-described conventional method was limited to the case where the gate insulating layer is formed of an oxide, had a problems that it could not be applied to the case where the gate insulating layer was formed of a substance other than the oxide.
Further, as a patent document related to the organic thin film transistor, there is Japanese Patent Laid-open No. 2003-255857 presented as Patent Document 1, for example.
Non-Patent Document 1
D. J. Gundlach, J. A. Nichols, L. Zhou and T. N. Jackson, Appl. Phys. Lett. 80, 2925 (2002)
Non-Patent Document 2
M. Shtein, J. Mapel, J. B. Benziger and S. Forrest, Appl. Phys. Lett. 81, 263 (2002)
Non-Patent Document 3
D. Knipp, R. A. Street, A. Volkel and J. Ho, J. Appl. Phys. 93, 347 (2003)
Non-Patent Document 4
J. Lee, K. Kim, J. H. Kim, S. Im and D. Jung, Appl. Phys. Lett. 82, 4169 (2003)
Non-Patent Document 5
I. Yagi, K. Tsukagoshi, Y. Aoagi, Appl. Phys. Lett. 86, 103502 (2005)
Patent Document 1
Japanese Patent Laid-open No. 2003-255857
The present invention has been created in view of the above-described problem that prior art has, and it is an object of the invention to provide an organic thin film transistor and a method for surface modification of the gate insulating layer of the organic thin film transistor, which is capable of modifying the surface of the gate insulating layer not only in the case where the gate insulating layer is formed of an oxide but also in the case where the gate insulating layer is formed of a substance other than the oxide, and consequently transistor characteristics can be significantly improved.
To achieve the above-described objects, the present invention is designed that a layer formed of polyparaxylylene (poly para-xylylene) is formed on the surface of the gate insulating layer.
The formation of polyparaxylylene layer on the surface of the gate insulating layer should only be performed by depositing polyparaxylylene film on the surface of the gate insulating layer by using a chemical vapor deposition (CVD), for example.
Herein, it is preferable that polyparaxylylene have high purity, that is, the purity of 99% or higher, and polychloroparaxylylene whose purity exceeds 99% can be used, for example.
According to the present invention, by the polyparaxylylene layer that is formed on the surface of the gate insulating layer formed of an oxide or a substance other than the oxide, the surface of the gate insulating layer is modified to hydrophobic, a threshold voltage becomes negative, Off can be taken when a gate voltage is zero, and stable operation can be obtained as a transistor.
Specifically, the present invention is an organic thin film transistor where an organic semiconductor layer is stacked on a gate insulating layer and an electrode is formed on the organic semiconductor layer, in which a polyparaxylylene layer formed of a continuous polyparaxylylene film is formed on the surface of the gate insulating layer, between the gate insulating layer and the organic semiconductor layer, so as to face and contact the organic semiconductor layer.
Further, the present invention, in the above-described invention is designed that the polyparaxylylene film is a continuous film whose film thickness shows the angle of 85 degrees or more by contact angle measurement of water.
Further, the present invention, in the above-described invention is designed that the polyparaxylylene has the purity of 99% or higher.
Further, the present invention, in the above-described invention is designed that the thickness of the polyparaxylylene film is 5 to 200 nm.
Further, the present invention, in the above-described invention is designed that the polyparaxylylene is polychloroparaxylylene.
Further, the present invention, in the method for surface modification of the gate insulating layer in the organic thin film transistor where the organic semiconductor layer is stacked on the gate insulating layer and the electrode is formed on the organic semiconductor layer is designed that the polyparaxylylene film is deposited on the surface of the gate insulating layer as continuous film having a predetermined thickness by chemical vapor deposition.
Further, the present invention, in the above-described invention is designed that the film thickness of the continuous film shows the angle of 85 degrees or more by the contact angle evaluation of water.
Further, the present invention, in the above-described invention is designed that the polyparaxylylene has the purity of 99% or higher.
Further, the present invention, in the above-described invention is designed that the film thickness of the continuous film is 5 to 200 nm.
Further, the present invention, the above-described invention is designed that the polyparaxylylene is polychloroparaxylylene.
Since the present invention is constituted as described above, the invention exerts an excellent effect that it can perform modification of the surface of the gate insulating layer not only in the case where the gate insulating layer is formed of an oxide but also in the case where the gate insulating layer is formed of a substance other than the oxide, and consequently transistor characteristics can be significantly improved.
a) (b) respectively show an organic thin film transistor by prior art and the organic thin film transistor by the present invention, in which
a) (b) (c) are explanatory views showing the state where the film observed by an optical microscope in arrow A of
a) (b) are graphs showing experiment results by the present inventor using the organic thin film transistor having the channel length L of 50 μ m by prior art, where
a) (b) are graphs showing experiment results by the present inventor using the organic thin film transistor having the channel length L of 50 μ m by the present invention, where
a) (b) (c) are graphs showing experiment results where the channel length dependency of a threshold voltage Vth, mobility and on/off ratio regarding the organic thin film transistor by prior art and the organic thin film transistor by the present invention each having the channel length L of 50 μ m, 100 μ m and 200 μ m were measured, where
a) (b) are explanatory views of an organic thin film transistor and the method for manufacturing the transistor, which uses a suspension bridge structure shown in Patent Application 2005-27034 (filing date: Feb. 2, 2005) “Method for manufacturing top-contact type field-effect transistor and top-contact type field-effect transistor”, where
a) (b) (c) are explanatory views showing a processing when applying the present invention to the organic thin film transistor using the suspended bridge structure, where
a) is an explanatory view showing the state where the SiO2 oxide film was observed by the atomic force microscope,
a) is an explanatory view showing the state where HMDS is observed by the atomic force microscope, and
a) is an explanatory view showing the state of observing the state where one water droplet was dropped on a “dix-C” (trademark) having the thickness of 10 nm formed on the SiO2 oxide film, and
Hereinafter, description will be made in detail for an example of the embodiments of the organic thin film transistor and the method for surface modification of the gate insulating layer in the organic thin film transistor according to the present invention by referring to the attached drawings.
Specifically, an organic thin film transistor 10 according to an example of the present invention is constituted by having: a substrate 12 formed of semiconductor, which is a gate layer that functions as a substrate and a gate electrode; a gate insulating layer 14 formed of an insulative material, which is formed on one surface 12a of the substrate 12; a polyparaxylylene film 16 being a polyparaxylylene layer, which is formed on the surface 14a of the gate insulating layer 14 by depositing polyparaxylylene; an organic semiconductor layer 18 being an active layer formed of an organic material, which is formed on the surface 16a of the polyparaxylylene film 16; a source electrode 20 being a first electrode formed of a conductive material, which is formed on the surface 18a of the organic semiconductor layer 18; and a drain electrode 22 being a second electrode formed of a conductive material, which is formed on the surface 18a of the organic semiconductor layer 18.
Specifically, in the organic thin film transistor 10, the polyparaxylylene film 16 and the organic semiconductor layer 18 face and contact with each other, and the polyparaxylylene film 16 is arranged directly under the organic semiconductor layer 18.
It is to be noted that the polyparaxylylene film 16 and the organic semiconductor layer 18 should only be formed by deposition, for example.
Herein, as the substrate 12, an n-type Si substrate being an Si substrate doped with phosphorus can be used, for example, but the substrate is not limited to this, and an n-type semiconductor substrate or a p-type semiconductor substrate where various impurities are doped in various semiconductor materials can be used.
Further, as the gate insulating layer 14, an SiO2 film being an insulative material can be used, for example, but the layer is not limited to this, and polymer film such as polyvinylphenol (PVP), polyvinylalcohol (PVA) and polystyrene (PS), for example, can be used instead of an oxide like SiO2.
Moreover, the polyparaxylylene film 16 is formed as a continuous film, that is, a continuous film having no holes formed therein, and it is preferable to form the film by high-purity polyparaxylylene, for example, more particularly polyparaxylylene whose purity is 99% or higher. Further, although the film thickness of the polyparaxylylene film is not particularly limited, it is preferable that the thickness be about 5 to 200 nm, more particularly about 5 to 100 nm. Particularly, in the case where the surface of the polyparaxylylene film 16 can be formed homogeneously, the film thickness can be made as thin as about 5 nm, for example.
It is to be noted that formation of a film whose surface is homogeneous is made possible by using high-purity polyparaxylylene.
Furthermore, as an organic material for forming the organic semiconductor layer 18, pentacene (Pentacene) can be used for example, but the material is not limited to this, and various organic materials such as copper phthalocyanine and thiophenes can be used, for example.
Further, the source electrode 20 and the drain electrode 22 can be formed by depositing metal being a conductive material which is Au, for example, by vapor deposition on the surface 18a of the organic semiconductor layer 18, for example, an Au electrode formed in this manner can be used as the source electrode 20 and the drain electrode 22. It is to be noted that a conductive material used as the source electrode 20 and the drain electrode 22 is not limited to Au, but Pt, Ag or the like can be used.
In the constitution above, in the above-described organic thin film transistor 10, the polyparaxylylene film 16 modifies the surface of the gate insulating layer 14 from hydrophilic to hydrophobic, and consequently, the transistor characteristics of the organic thin film transistor 10 could be significantly improved.
Next, description will be made for the experiment and its result by the present inventor, the organic thin film transistor by prior art and the organic thin film transistor by the present invention were fabricated in this experiment, and the transistor characteristics of the both transistors were compared.
First, description will be made for the manufacturing methods of the organic thin film transistor by prior art and the organic thin film transistor by the present invention used in the experiment. As the substrate 12, 6 pieces of n-type Si substrates where the SiO2 thermal oxide film having the thickness of 200 nm as the gate insulating layer 14 was formed on one surface were prepared and oxygen plasma cleaning was performed after solution cleaning by acetone and isopropyl alcohol was performed.
Regarding 3 pieces of n-type Si substrate out of the 6 pieces of the n-type Si substrate to which the above-described processing was performed, only on the surface of their SiO2 thermal oxide film, a film formed of high-purity polychloroparaxylylene (poly chloro-para-xylylene) having the purity of 99% or higher was deposited as the polyparaxylylene film 16 by chemical vapor deposition (CVD) to so to be formed in the thickness of 10 nm.
Meanwhile, in this experiment, “dix-C” (trademark) that is one of polyparaxylylene, which is generally called as “diX” (trademark) manufactured by Daisan Kasei Co., Ltd., was used as the high-purity polychloroparaxylylene having the purity of 99% or higher. It is to be noted that “diX” (trademark) has purity exceeding 99%.
Further, to deposit “dix-C” (trademark) on the surface of the SiO2 thermal oxide film by chemical vapor deposition in this experiment, it was performed under reduced pressure by using an exclusive unit called “DACS-0” (trademark) manufactured by KISCO Ltd., which is used for coating “diX” (trademark) manufactured by Daisan Kasei Co., Ltd. This unit mainly consists of the 3 portions of a vaporizer, a pyrolizer and a deposition chamber, where the n-type Si substrate on which the SiO2 thermal oxide film is formed is arranged in the deposition chamber, and powder of “dix-C” (trademark) being the coating material is arranged in the vaporizer. Then, after decompressing inside the unit, the temperature of the vaporizer is increased (120 to 180° C.) to evaporate “dix-C” (trademark). When the evaporated gas is drawn by a vacuum pump to flow toward the deposition chamber side, and passes through the high-temperature (650 to 700° C.) pyrolizer, the gas is thermally decomposed into monomer. Moreover, when the monomer contacts the SiO2 thermal oxide film inside the deposition chamber of room temperature, it is cooled down and polymerized on the surface, and a high-molecular weight polyparaxylylene film is formed on the surface of the SiO2 thermal oxide film.
Then, on the above-described 6 pieces of n-type Si substrates, pentacene film having the thickness of 30 nm was vacuum-deposited as the organic semiconductor layer 18 through a metal mask.
Next, the metal mask was replaced, an Au film having the thickness of 50 nm as the source electrode 20 and the drain electrode 22 was formed on the surface of the pentacene film vacuum-deposited as described above, and thus a three organic thin film transistor according to prior art (refer to
Herein, the three organic thin film transistors by prior art (refer to
Therefore, according to the above-described manufacturing method, the three organic thin film transistor by prior art having the channel length L of 200 μ m, 100 μ m or 50 μ m, and similarly, the three organic thin film transistor by the present invention having the channel length L of 200 μ m, 100 μ m or 50 μ m were obtained.
It is to be noted that the degree of vacuum during deposition is 2×10−4 Pa for all cases in the above-described manufacturing method.
First, the output characteristics and the transfer characteristics of the transistor were measured by using the organic thin film transistor by prior art having the channel length L of 50 μ m (refer to
Herein,
The measurement result took the threshold voltage Vth of +10V and the threshold voltage Vth of a positive value as shown in
It is to be noted that the mobility of transistor is 0.069 cm2/Vs and the on/off ratio is 6.4×103.
Further, in the organic thin film transistor by prior art having the channel length L of 50 μ m, as shown in the graph of
On the other hand,
Herein,
It is to be noted that the mobility of transistor is 0.17 cm2/Vs and the on/off ratio is 8.9×104.
Further, in the organic thin film transistor by the present invention having the channel length L of 50 μ m, as shown in the graph of
Next, by using the organic thin film transistor by prior art and the organic thin film transistor by the present invention each having the channel length L of 50 μ m, 100 μ m and 200 μ m, each channel length dependency for the threshold voltage Vth, the mobility and the on/off ratio was measured.
a)(b)(c) show the measurement result, where
As shown in the graphs of
Herein,
The polyparaxylylene film having the thickness of 10 nm formed of “dix-C” (trademark) has:
Meanwhile, for reference, the SiO2 thermal oxide film formed on the n-type Si substrate had Root-mean-square roughness (RMS)=0.158 nm.
Further, since the polyparaxylylene film has characteristics that it thoroughly grows around the surface of an object, the present invention can be applied to a transistor having the shape described below, which is proposed by the present applicant.
Specifically, the present applicant proposes the organic thin film transistor using the suspended bridge structure and the method for manufacturing the transistor that will be described referring to
To fabricate the organic thin film transistor using the suspension bridge structure, firstly, a solid suspended bridge structure formed of a three-layered structure by resist 106 is formed on an n-type Si substrate 102 (corresponding to the substrate 12) where an SiO2 oxide film 104 (corresponding to the gate insulating layer 14) having the thickness of 50 nm is formed on one surface as the gate insulating layer by using electron beam lithography technology (refer to
Then, to the n-type Si substrate 102 where the resist 106 including the suspended bridge structure was formed on the SiO2 oxide film 104, by performing a first process of depositing a pentacene film 108 (corresponding to the organic semiconductor layer 18) at the deposition angle of 45 degrees to a vertical direction (refer to
It is to be noted that a channel is formed under the suspended bridge structure in such an organic thin film transistor using the suspended bridge structure.
Herein, in applying the present invention to the above-described organic thin film transistor using the suspended bridge structure, as shown in
Then, the first process to the third process shown in
Next, the transfer characteristics of the transistor was measured by using the organic thin film transistor including the structure shown in
On the other hand,
Herein, description will be made for a measurement result by a contact angle measurement method for evaluating water contact angle where the water contact angle of “dix-C” (trademark) the polyparaxylylene film 16 was measured.
It is to be noted that the water contact angle measurement method is a measurement method where one water droplet is dropped on a substrate and a contact angle of water edge with the substrate is measured.
Herein, for comparison, measurement was also performed for the SiO2 oxide film formed on the Si substrate and HMDS coated on the surface of the SiO2 oxide film that was formed on the Si substrate by spin coating.
The root-mean-square roughness (RMS) of the SiO2 film was 0.1580 nm, and the water contact angle was 6.8 degrees.
Further,
The root-mean-square roughness (RMS) of the HMDS was 0.1638 nm, and the water contact angle was 70 degrees.
Then,
Regarding “dix-C” (trademark), the water contact angle was 87 degrees for the both cases of film thickness 10 nm and 415 nm. Specifically, the water contact angle does not change even if the film thickness of “dix-C” (trademark) is made thin or thick.
Herein, although the water contact angle needs to be larger in order to modify the surface of the gate insulating layer 14 into hydrophobic, the water contact angle does not change even if the film thickness of “dix-C” (trademark) is made thin or thick, and the water contact angle of 85 degrees or larger is obtained even with the film thickness of about 5 nm if the polyparaxylylene film 16 is a continuous film, and the surface of the gate insulating layer 14 is modified into hydrophobic.
It is to be noted that the above-described embodiment may be modified as described in (1) to (3) below.
(1) In the above-described embodiment, polychloroparaxylylene whose purity exceeds 99% was shown as an example of polyparaxylylene, it goes out without saying that the material is not limited to this, and polyparaxylylene derivative using 4-amino(2,2)paracyclophane, 4-aminomethyl(2,2)paracyclophane, tetrachloro(2,2)paracyclophane, 1,1,9,9-tetrafluoro(2,2)paracyclophane or the like as an initial material can be used.
(2) In the above-described embodiment, specific material names and thickness have been shown regarding the substrate 12, the gate insulating layer 14, the organic semiconductor layer 18, the source electrode 20 and the drain electrode 22, but it goes without saying that the materials and the thickness are merely examples, and it is a matter of course that materials and the thickness may be appropriately selected corresponding to design conditions or the like.
(3) The modification examples shown in the above-described embodiment and above-described (1) to (2) may be appropriately combined.
The present invention can be used in manufacturing a flexible display, a fine organic electronic device, a nano-bio device and the like which are used in electronic equipment, medical equipment and the like.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-252256 | Aug 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2006/316687 | 8/25/2006 | WO | 00 | 7/28/2008 |
