WO2010117021A1 - 電界効果トランジスタ、その製造方法及びそれを用いた電子デバイス - Google Patents
電界効果トランジスタ、その製造方法及びそれを用いた電子デバイス Download PDFInfo
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- WO2010117021A1 WO2010117021A1 PCT/JP2010/056325 JP2010056325W WO2010117021A1 WO 2010117021 A1 WO2010117021 A1 WO 2010117021A1 JP 2010056325 W JP2010056325 W JP 2010056325W WO 2010117021 A1 WO2010117021 A1 WO 2010117021A1
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- effect transistor
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/417—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions carrying the current to be rectified, amplified or switched
- H01L29/41725—Source or drain electrodes for field effect devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66015—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene
- H01L29/66037—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66045—Field-effect transistors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
- H10K10/82—Electrodes
- H10K10/84—Ohmic electrodes, e.g. source or drain 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
- H10K71/10—Deposition of organic active material
- H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. 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
- H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
Definitions
- the present invention relates to a field effect transistor, a manufacturing method thereof, and an electronic device using the same.
- a coating type semiconductor material capable of forming a semiconductor layer by a coating process has an advantage that a large-area electronic device can be manufactured at low cost and low energy without requiring expensive equipment.
- Patent Document 1 describes that a field effect transistor is obtained by applying a bicyclo compound on a substrate and converting it to a semiconductor material. This method removes ethylene by heating a highly soluble bicyclo compound and converts it to a highly planar structure, thereby forming an organic semiconductor layer having high crystallinity from an amorphous or near-organic thin film. To do. Therefore, it is possible to form a film by a coating process with a low molecular weight, and it is possible to form a field effect transistor having higher mobility.
- Patent Document 2 describes that in a source / drain electrode having a tapered portion on the channel side, the contact resistance can be reduced by making the tapered portion width in the channel length direction shorter than the average grain size of the semiconductor crystal.
- the source / drain electrodes made of a Cr adhesive layer and Au are formed so that the angle formed with the substrate (taper angle) is 45 ° or more, and the width of the tapered portion is formed by vacuum deposition.
- the contact resistance is reduced by making it smaller than 50 nm, which is the average size of the pentacene crystal formed above.
- Patent Document 2 as a prior art, a transistor having a tapered source / drain electrode is described in Patent Document 3 and Patent Document 4, but Patent Document 3 describes an interface or drain electrode between a source electrode and a semiconductor layer.
- Patent Document 3 describes an interface or drain electrode between a source electrode and a semiconductor layer.
- Japanese Unexamined Patent Publication No. 2003-304014 Japanese Unexamined Patent Publication No. 2005-93542 Japanese Unexamined Patent Publication No. 2008-66510 Japanese Unexamined Patent Publication No. 2007-266355
- the conventional field effect transistor has a problem that the mobility is insufficient or the mobility varies.
- the substrate on the side surface facing the channel region of the source / drain electrode in a cross section parallel to the channel length direction and perpendicular to the substrate It has been found that when the angle with respect to is large, the mobility decreases, and there is a problem that the mobility varies.
- the present invention was devised in view of the above problems, and an object of the present invention is to provide a method for increasing the mobility of a field effect transistor using a coating type semiconductor material and further suppressing variation in mobility.
- the present inventors have found that in a field-effect transistor having a semiconductor layer formed by a coating process, the source in a cross section parallel to the channel length direction and perpendicular to the substrate The inventors have found that by forming these electrodes so that the drain electrode has a taper, it is possible to improve mobility and further suppress variation in mobility, thereby completing the present invention. That is, this invention exists in the following structure.
- a field effect transistor having at least a substrate, a semiconductor layer formed by a coating method, a source electrode, and a drain electrode, and having a source electrode and / or a cross section parallel to the channel length direction and perpendicular to the substrate
- the semiconductor is an organic semiconductor having an annulene structure.
- variation in mobility is ⁇ 30% or less.
- a method of manufacturing a field effect transistor including a step of forming a source electrode and / or a drain electrode so as to include a step of applying a coating solution containing a semiconductor.
- the formation of the tapered source electrode and / or drain electrode is performed by forming a photoresist layer in two stages, exposing the uncured portion, forming a metal layer, and then removing the unnecessary metal layer by the lift-off method.
- a field effect transistor having at least a substrate, a semiconductor layer formed by a coating method, a source electrode, and a drain electrode, the source electrode and / or the cross section parallel to the channel length direction and perpendicular to the substrate
- a method for improving mobility of a field effect transistor by forming a source electrode and / or a drain electrode so that the drain electrode has a taper.
- a field effect transistor using a coating type semiconductor material in a field effect transistor using a coating type semiconductor material, a field effect transistor having a high mobility and a small mobility variation can be obtained.
- FIG. 2 is a cross-sectional SEM image of a two-layer resist in Example 1.
- FIG. 2 is a cross-sectional SEM image of a source / drain electrode in Example 1.
- FIG. 2 is a polarization micrograph of a field effect transistor in Example 1.
- FIG. 6 is a cross-sectional SEM image of a source / drain electrode in Example 2.
- 6 is a cross-sectional TEM image of a source / drain electrode in Comparative Example 1.
- FIG. 6 is a graph of average mobility and taper angle of a field effect transistor having a Cr adhesive layer and a source / drain electrode made of Au. It is a graph of variation in mobility and taper angle of a field effect transistor having a Cr adhesive layer and a source / drain electrode made of Au.
- One embodiment of the present invention is a field effect transistor having at least a substrate, a semiconductor layer formed by a coating method, a source electrode, and a drain electrode, and in a cross section parallel to the channel length direction and perpendicular to the substrate,
- the source electrode and / or the drain electrode have a taper, and the angle of the taper with respect to the substrate is 70 ° or less.
- the source electrode and / or drain electrode of the present invention has a taper in a cross section parallel to the channel length direction and perpendicular to the substrate, and the angle of the taper with respect to the substrate is 70 ° or less.
- the “channel region” means a region where the source electrode and the drain electrode face each other and are sandwiched between these electrodes
- the “channel length” means the distance between the source electrode and the drain electrode.
- “Long direction” refers to a direction connecting the source electrode and the drain electrode. Therefore, the “cross section parallel to the channel length direction and perpendicular to the substrate” of the present invention corresponds to the “cross section” as shown in the cross-sectional view of FIG. 1, and in the present invention, as shown in FIG. In addition, in the cross section, the source electrode and / or the drain electrode have a taper.
- taper means a shape with a tapered tip, and therefore “the source electrode and / or drain electrode has a taper in the cross section” means “source electrode and / or drain electrode”. Means that the side surface of the source electrode and / or the drain electrode facing the channel region is inclined with respect to the substrate.
- the angle of the taper with respect to the substrate means the angle of the side surface facing the channel region of the source electrode and / or drain electrode with respect to the substrate (as described above, This is sometimes referred to as a “taper angle”.
- the angle of the taper with respect to the substrate (taper angle)” in the present invention refers to the tip of the electrode and the electrode facing the channel region in a cross section parallel to the channel length direction and perpendicular to the substrate.
- the straight line connecting a point at a height of 10 nm from the bottom surface of the side surface is defined as an angle formed with the gate insulating film plane.
- FIG. 1 shows a method for measuring a taper angle according to the present invention.
- the tip of the electrode and a point at a height of 10 nm from the bottom of the electrode side surface can be set, and the angle can be measured.
- the taper angle exceeds 90 °, it is “reverse taper” and is distinguished from “taper” of the present invention.
- the taper angle By making the taper angle smaller, the mobility of a field effect transistor using a coated semiconductor material can be improved, and variation in mobility can be reduced. This is presumed to be that by reducing the angle, it is possible to suppress the formation of voids between the source / drain electrodes and the semiconductor layer when the coated semiconductor is formed or when the semiconductor layer is contracted by heating.
- mobility refers to the output characteristics of a manufactured semiconductor element measured in dry nitrogen using an Agilent 4155c semiconductor parameter analyzer, and ⁇ I d sat and V g using the following equation (1). This is a value obtained from the slope of the straight line.
- I d sat is the drain current
- W is the channel width
- C i is the capacitance of the gate insulating film
- L is the channel length
- ⁇ sat is the mobility
- V g is the gate voltage
- V th is It is a threshold voltage.
- mobility variation refers to how much the mobility of five samples prepared and measured under the same conditions is distributed within the average mobility value.
- variation in mobility of a field effect transistor using a coating-type semiconductor material can be ⁇ 30% or less, preferably ⁇ 10% or less.
- the source electrode and / or the drain electrode have a taper in a cross section parallel to the channel length direction and perpendicular to the substrate, that is, if the angle of the taper to the substrate (taper angle) is less than 90 °.
- the effect of the present invention it is preferable at 70 ° or less because an excellent mobility improving effect and mobility variation reducing effect can be obtained. More preferably, it is 45 ° or less, and more preferably 30 ° or less. If the angle is too large, the semiconductor layer and the electrode may not be properly joined when the coating type semiconductor material is formed, or the semiconductor layer is contracted due to crystallization or heating after the film formation. In some cases, voids may be formed in the substrate, which adversely affect the semiconductor characteristics. Further, if the angle of the taper with respect to the substrate (taper angle) is larger than 0 °, the effect of the present invention is obtained, and is substantially 0.1 ° or more.
- the type of the source / drain electrode of the present invention is not particularly limited. Specifically, metals and alloys such as Au, Co, Cu, Ir, Mo, Ni, Pd, Pt, Te, and W can be used. Further, an oxide layer may be formed on the surface of the source / drain electrodes by heating the surface of these metals in air or in an oxygen atmosphere, or by performing UV / ozone treatment or O 2 plasma treatment. In addition, metal oxides such as MoO x , NiO x , CoO x , CuO x , ITO, IZO, IWZO, and IGZO may be used.
- An electrode adhesive layer can be adjacent to the source / drain electrodes.
- the electrode adhesive layer is not particularly limited, and specifically, metal and alloys such as Cr, Mo, Ni, Ti, and metal oxides such as MoO x , NiO x , CuO x , MoO x , MnO x are used. You may do it.
- the work function of the surface of the source, drain electrode, or electrode adhesive layer is preferably 4.5 eV or more. More preferably, it is 5.0 eV or more.
- the upper limit is not particularly limited, but is preferably 10 eV or less.
- the source electrode and / or the drain electrode are formed to have a taper in a cross section parallel to the channel length direction and perpendicular to the substrate (hereinafter, such an electrode is referred to as a “tapered electrode”). Sometimes called). A method for manufacturing such an electrode will be described. Tapered source / drain electrodes are formed by forming a photoresist on a lower resist layer that does not have photosensitivity, and controlling the development time after exposure so that the upper photoresist layer extends like an eave.
- the shape of the taper can be controlled by changing the shape of the lift-off resist, the electrode material film forming method, the film forming conditions, and the like. Further, it can be controlled by changing the composition of the etching gas and the etching solution. In the printing process, a tapered shape can be formed by controlling the surface tension and viscosity of the conductive ink, the surface energy of the insulating film, and the like.
- the type of the substrate of the present invention is not particularly limited, and specifically, inorganic materials such as glass and quartz, insulating plastics such as polyimide film, polyester film, polyethylene film, polyphenylene sulfide film, and polyparaxylene film, inorganic Hybrid substrates combining materials, metal / alloy plates, insulating plastics, etc. can be used. Also, a gate insulating film and a substrate which will be described later may be integrated, such as a conductive n-type silicon wafer.
- the semiconductor layer of the present invention is formed by a coating method.
- a coating method By forming the semiconductor layer by a coating method, a field effect transistor can be manufactured at a lower cost than the formation of a semiconductor layer by a vacuum process.
- the influence of the base on the crystallization of the semiconductor is reduced as compared with the case where the semiconductor layer is formed by vacuum vapor deposition, and the difference in crystal growth on the insulating film and the source / drain electrodes is reduced. Therefore, by forming the source / drain electrodes in a tapered shape, crystal growth between the source / drain electrodes and the gate insulating film is promoted, and a gap is formed between the tip of the electrode important for charge injection and the semiconductor layer. It becomes difficult.
- the coating method is not particularly limited, and examples thereof include spin coating, inkjet, aerosol jet printing, microcontact printing, dip pen method, screen printing, letterpress printing, intaglio printing, and gravure offset printing. *
- the method for forming the semiconductor layer by a coating method is not particularly limited. Specifically, (a) a method of applying a coating solution containing a semiconductor and forming a semiconductor layer after drying, and (b) a semiconductor precursor.
- coating the coating liquid containing a body, and converting into a semiconductor after that and making it a semiconductor layer is mentioned.
- the method (a) since crystallization occurs with the drying of the solvent, the crystal growth tends to change depending on the drying conditions of the solvent.
- the method (b) is advantageous in that since a precursor film is formed once, crystallization occurs, so that the crystallization conditions are easily fixed and a uniform crystal film is easily obtained.
- a semiconductor there is no particular limitation as a semiconductor. It may be a p-type semiconductor, an n-type semiconductor, or an organic semiconductor material or an inorganic semiconductor material.
- the organic material include acenes such as pentacene, heterocycle-containing condensed ring aromatic compounds such as benzothiophene, and annulene compounds such as porphyrin and phthalocyanine, and among them, annulene compounds such as porphyrin and phthalocyanine are preferable.
- the inorganic material include oxide semiconductors such as silicon and ZnO.
- the semiconductor precursor is not particularly limited as long as it has semiconductor characteristics by conversion, and the conversion method is not particularly limited.
- an anurene compound an acene (eg, naphthalene, anthracene, pentacene, etc.), an aromatic oligomer (eg, a naphthalene, anthracene, etc.) having a heat / light conversion bicyclo structure that causes a reverse Diels-Alder reaction by heating or light irradiation.
- Oligothiophene, oligofuran, etc. heterocondensed ring-containing aromatic compounds (for example, benzothiophene, thienothiophene, etc.) and the like.
- the inorganic material examples include cyclopentasilane that opens by light irradiation.
- it is a heat conversion type bicyclo structure which causes reverse Diels-Alder reaction by heating, and among them, bicycloporphyrins represented by formula (I) are preferable.
- the semiconductor precursor is converted into a semiconductor by heating, light irradiation or the like.
- Conversion conditions can be appropriately selected according to the type of the precursor. For example, a porphyrin having a heat conversion type bicyclo structure that causes a reverse Diels-Alder reaction by heating is converted as shown in formula (I), but is converted under a heating condition of 150 ° C. or higher.
- the compounds shown below are also semiconductor precursors that are converted to pentacene or PTV (polythienylene vinylene) having semiconductor characteristics by heating, and can be effectively used in the present invention.
- the gate electrode of the present invention is not particularly limited, but specifically, conductive n-type Si wafers, metals such as Ta, Al, Cu, Cr, Mo, W, Ti, alloys of these metals, and laminated layers Conductive polymers such as films, polyaniline, polypyrrole, and PEDOT, and conductive ink using metal particles can also be used.
- Gate insulation layer There is no particular limitation on the type of the gate insulating film of the present invention. Specifically, an insulating polymer such as polyimide, polyvinylphenol, polyvinyl alcohol, or epoxy may be applied and baked, or SiO 2 , SiN x , aluminum oxide, tantalum oxide, or the like may be formed by CVD or sputtering. When tantalum or aluminum is used for the gate electrode, tantalum oxide or aluminum oxide formed on the surface of the gate electrode by UV / ozone treatment or anodizing treatment may be used.
- an insulating polymer such as polyimide, polyvinylphenol, polyvinyl alcohol, or epoxy may be applied and baked, or SiO 2 , SiN x , aluminum oxide, tantalum oxide, or the like may be formed by CVD or sputtering.
- tantalum oxide or aluminum oxide formed on the surface of the gate electrode by UV / ozone treatment or anodizing treatment may be used.
- FIG. 2 is a schematic sectional view of a bottom contact / bottom gate field effect transistor using the present invention.
- Other structures of the field effect transistor using the present invention include a bottom contact / top gate type and a top / bottom contact type. Further, a dual gate type having gate electrodes above and below the source / drain electrodes may be used.
- the field effect transistor of the present invention can be used for electronic devices and photoelectric devices.
- An electronic device is preferable. Specific examples of the electronic device include a display element, an electronic tag, an electromagnetic wave, and a pressure sensor.
- the gate insulating film capacitance (C i ) is 1.15 ⁇ 10 ⁇ 4 F / m 2 with a dielectric constant of 3.9.
- polymethylglutarimide (PMGI) resist (SF-9 manufactured by Kayaku Microchem Corp.) was spin-coated to a thickness of 0.5 ⁇ m on the thermally oxidized silicon film and heated at 180 ° C. for 5 minutes.
- a negative photoresist (ZPN-1150 made by Nippon Zeon Co., Ltd.) was spin-coated on the resist film to a thickness of 4 ⁇ m, heated at 80 ° C. for 180 seconds, then exposed for 40 seconds and heated at 110 ° C. for 120 seconds. Thereafter, development was performed with an organic alkali developer (NPD-18 manufactured by Nagase ChemteX Corporation) to form a two-layer resist pattern in which the upper resist protruded from the lower resist. The cross-sectional SEM image (observation magnification 50,000 times) of was shown.
- FIG. 4 shows a cross-sectional SEM image of the obtained field effect transistor.
- the angle of the taper with respect to the substrate was 1 °.
- FIG. 5 shows a polarizing microscope photograph of the obtained field effect transistor (magnification 150 times). There is almost no difference in the size of the semiconductor crystal on the Mo source / drain electrode and on the SiO 2 gate insulating film. An organic semiconductor crystal grows between the source / drain electrodes and the gate insulating film. In the video observation of crystal growth, it was observed that crystal growth occurred between the source / drain electrodes and the gate insulating film, regardless of whether crystal nuclei were generated from the source / drain electrodes or the gate insulating film. .
- Example 1 except that instead of the Mo electrode, a 5 nm Cr adhesive layer and 100 nm Au were formed on the two-layer resist pattern by vacuum deposition by electron beam heating and resistance heating, respectively.
- a field effect transistor was prepared in the same manner as described above. In the obtained field effect transistor, when five samples were measured at a channel length of 13 ⁇ m and a channel width of 500 ⁇ m, the mobility was 0.77 cm 2 / V ⁇ s on average, and the variation in mobility was ⁇ 10%.
- FIG. 6 shows a cross-sectional SEM image of the obtained field effect transistor. When measured at an observation magnification of 50,000, the angle of the taper with respect to the substrate was 70 °.
- Example 1 instead of ZPN-1150, positive type OFPR-800LB was formed on SF-9 to a thickness of 1 ⁇ m, and photolithography and development were performed.
- the electric field was changed in the same manner as in Example 1 except that a 5 nm Cr adhesive layer and 100 nm Au were formed by vacuum deposition by electron beam heating and resistance heating on the two-layer resist pattern in place of the Mo electrode.
- An effect transistor was created.
- the obtained field effect transistor when five samples were measured at a channel length of 12 ⁇ m and a channel width of 500 ⁇ m, a high mobility of 0.70 cm 2 / V ⁇ s on average was obtained, and the variation in mobility was ⁇ 20%.
- the angle of the taper with respect to the substrate was 45 °.
- Example 1 a field effect transistor was prepared in the same manner as in Example 1 except that a 5 nm Cr adhesion layer and 100 nm Au were formed on the two-layer resist pattern by sputtering.
- the mobility when five samples were measured at a channel length of 12 ⁇ m and a channel width of 500 ⁇ m, the mobility was 0.92 cm 2 / V ⁇ s on average, and the variation in mobility was ⁇ 20%.
- the angle of the taper with respect to the substrate was 1 °.
- Example 1 Comparative Example 1
- PMGI polymethylglutarimide
- ZPN-1150 manufactured by Nippon Zeon Co., Ltd.
- ZPN-1150 manufactured by Nippon Zeon Co., Ltd.
- a field effect transistor was prepared.
- the obtained field effect transistor had a mobility of 0.28 cm 2 / V ⁇ s on average and a variation of ⁇ 40% when five samples were measured at a channel length of 13 ⁇ m and a channel width of 500 ⁇ m. Further, when measured at a TEM observation magnification of 100,000, the angle of the taper with respect to the substrate was 130 ° (reverse taper).
- FIG. 7 shows a cross-sectional TEM image of the field effect transistor obtained in Comparative Example 1.
- the source / drain electrodes are formed in a reverse taper shape with respect to the substrate plane in the lower portion, and a gap is formed between the source / drain electrodes and the semiconductor layer in the vicinity of the insulating film. In the case where a gap is generated between the source / drain electrodes and the semiconductor layer, charge injection does not occur in that portion, the mobility is lowered, and further, the semiconductor characteristics vary.
- Comparative Example 2 In Comparative Example 1, a field effect transistor was prepared in the same manner as in Comparative Example 1 except that the exposure time was 15 seconds. The obtained field effect transistor was measured for five samples at a channel length of 10 ⁇ m and a channel width of 500 ⁇ m. The mobility was 0.55 cm 2 / V ⁇ s on average and the variation was ⁇ 50%. The angle of the taper with respect to the substrate was 90 °.
- FIG. 8 shows a graph of mobility and taper angle of a field effect transistor having a Cr adhesive layer and an Au electrode and having a bicyclobenzoporphyrin formed into a semiconductor
- FIG. 9 shows the Cr adhesive layer and the Au electrode.
- 5 is a graph of variation in field effect transistor mobility and taper angle.
- Comparative Example 3 In Comparative Example 1, except that heat conversion type bicycloporphyrin was used, pentacene was deposited by vacuum deposition at a rate of 1 ⁇ / s so as to have a film thickness of 50 nm, and a semiconductor layer was formed. A field effect transistor was prepared in the same manner as described above. The angle of the taper with respect to the substrate was 130 ° (reverse taper). The obtained field effect transistor had a mobility of 0.0088 cm 2 / V ⁇ s on average when three samples were measured at a channel length of 13 ⁇ m and a channel width of 500 ⁇ m.
- Comparative Example 4 In Comparative Example 2, a field effect transistor was prepared in the same manner as in Comparative Example 2 except that pentacene was formed by vacuum deposition in place of the heat conversion type bicycloporphyrin and a semiconductor layer was formed. The angle of the taper with respect to the substrate was 90 °. When three samples were measured for the obtained field effect transistor at a channel length of 10 ⁇ m and a channel width of 500 ⁇ m, the average mobility was 0.014 cm 2 / V ⁇ s.
- Example 5 a field effect transistor was prepared in the same manner as in Example 2 except that pentacene was formed by vacuum deposition in place of the heat conversion type bicycloporphyrin and a semiconductor layer was formed. The angle of the taper with respect to the substrate was 70 °. The obtained field effect transistor had a mobility of 0.0028 cm 2 / V ⁇ s on average when three samples were measured at a channel length of 13 ⁇ m and a channel width of 500 ⁇ m.
- Example 6 a field effect transistor was prepared in the same manner as in Example 3 except that instead of the heat conversion type bicycloporphyrin, pentacene was formed by vacuum deposition to form a semiconductor layer. The angle of the taper with respect to the substrate was 45 °. The obtained field effect transistor had a mobility of 0.0070 cm 2 / V ⁇ s on average when three samples were measured at a channel length of 12 ⁇ m and a channel width of 500 ⁇ m.
- a field-effect transistor with high mobility and low mobility variation can be obtained.
- the field effect transistor of the present invention can be used in various electronic devices such as flat panel displays, flexible displays, electronic tags, and light / pressure sensors.
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Abstract
Description
一方、塗布プロセスによって半導体層を形成できる塗布型半導体材料は、大面積の電子デバイスを高価な設備を必要とせず低コスト、低エネルギーで製造できる利点がある。
(2)半導体がアヌレン構造の有機半導体である上記(1)に記載の電界効果トランジスタ。
(3)移動度のばらつきが±30%以下である上記(1)又は(2)に記載の電界効果トランジスタ。
(5)少なくとも基板、半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタの製造方法であって、チャネル長方向に平行でかつ基板に対して垂直な断面においてソース電極及び/又はドレイン電極がテーパーを有するように、ソース電極及び/又はドレイン電極を形成する工程、半導体の前駆体を含有する塗布液を塗布する工程、並びに、加熱及び/又は光照射により該前駆体を半導体に変換する工程を含む電界効果トランジスタの製造方法。
(7)上記(4)~(6)のいずれかに記載の方法により製造された電界効果トランジスタ。
(9)上記(1)~(3)及び(7)のいずれかに記載の電界効果トランジスタを用いた電子デバイス。
本発明の一つの態様は、少なくとも基板、塗布法によって形成される半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタであって、チャネル長方向に平行でかつ基板に対して垂直な断面において、ソース電極及び/又はドレイン電極がテーパーを有し、該テーパーの前記基板に対する角度が70°以下である電界効果トランジスタである。
本発明のソース電極及び/又はドレイン電極は、そのチャネル長方向に平行でかつ基板に対して垂直な断面において、テーパーを有し、該テーパーの前記基板に対する角度が70°以下であることを特徴とする。
具体的には、本発明の「テーパーの基板に対する角度(テーパー角)」は、チャネル長方向に平行でかつ基板に対して垂直な断面において、電極の先端部と、上記チャネル領域に面した電極側面の底面から高さ10nmにおける点とを結んだ直線が、ゲート絶縁膜平面となす角度と定義する。図1に本発明のテーパー角の測定方法を示した。電極断面を5万倍以上のSEM写真で撮影することにより、電極の先端部と、上記電極側面の底部から高さ10nmにおける点とを設定し、上記角度を測定することができる。なおここで、上記テーパー角が90°を超える場合は「逆テーパー」であり、本発明の「テーパー」とは区別される。
なお、p型半導体の場合、ソース、ドレイン電極、または電極接着層の表面の仕事関数は、4.5eV以上であることが好ましい。さらに好ましくは、5.0eV以上である。上限は特に限定はないが、10eV以下が好ましい。
テーパー形状のソース・ドレイン電極の形成は、感光性を持たない下層レジスト上にフォトレジストを製膜し、露光後の現像時間を制御することによって上層のフォトレジストがひさしのように張り出した形状を形成させた2層レジストを使用したリフトオフ法、単体でオーバーハング形状を作ることができるフォトレジストを用いたリフトオフ法、等方性のエッチング液を使用したウェットエッチング、等方性のエッチングガスを使用したドライエッチング、フォトレジストの末端をテーパー形状にしたり、レジストの膜減りを利用したドライエッチング、もしくはインクの粘度及びゲート絶縁膜の表面エネルギー等を制御したインクジェット等の印刷法等を用いることができる。テーパーの形状は、リフトオフレジストの形状および電極材料の製膜方法および製膜条件等を変えることにより制御することができる。さらに、エッチングガスおよびエッチング液の組成等を変更することにより制御することができる。印刷プロセスにおいては、導電性インクの表面張力および粘性、絶縁膜の表面エネルギー等を制御することで、テーパー形状を形成することができる。
本発明の基板の種類は特に限定はないが、具体的には、ガラス、石英等の無機材料や、ポリイミド膜、ポリエステル膜、ポリエチレン膜、ポリフェニレンスルフィド膜、ポリパラキシレン膜等の絶縁プラスチック、無機材料、金属・合金板、絶縁プラスチックを組み合わせたハイブリッド基板等が使用可能である。又、導電性n型シリコンウェハーのように、後述のゲート絶縁膜と基板が一体になったものを用いても構わない。
本発明の半導体層は、塗布法によって形成されることを特徴とする。
塗布法によって半導体層を形成することで、真空プロセスによる半導体層の形成に比べ、低コストで電界効果トランジスタを製造することができる。また、真空蒸着法により半導体層を形成した場合に比べ、半導体の結晶化に対する下地の影響が小さくなり、絶縁膜上とソース・ドレイン電極上における結晶成長の違いが縮小する。そのため、ソース・ドレイン電極をテーパー形状とすることにより、ソース・ドレイン電極とゲート絶縁膜間に跨った結晶成長が促進され、電荷注入に重要な電極の先端部と半導体層の間に空隙が生じ難くなる。
(a)の方法においては、溶媒の乾燥と共に結晶化が生じる為、溶媒の乾燥条件等により結晶成長に変化が生じ易い。一方、(b)の方法は一旦前駆体の膜を形成した後に、結晶化を起こす為、結晶化条件を一定にし易く、均一な結晶膜を得易いという利点がある。ただし、置換基の脱離による分子サイズの減少、及び高い結晶性により半導体膜の収縮が大きいため、結晶化過程においてソース・ドレイン電極と半導体層の間に空隙が生じ易い問題が有る。しかし、本発明に従いソース・ドレイン電極をテーパー形状とすることにより、半導体層のソース・ドレイン電極とゲート絶縁膜間に跨る結晶成長を促進することができるため、結晶化過程におけるソース・ドレイン電極と半導体層間の空隙生成を抑制することが可能である。そのため、本発明では、(b)半導体の前駆体を含有する塗布液を塗布し、その後半導体に変換して半導体層とする方法において、より良好な効果が得られる。
本発明のゲート電極としては、特に限定はないが、具体的には導電性n型Siウェハー、Ta、Al、Cu、Cr、Mo、W、Ti等の金属や、これらの金属の合金および積層膜、ポリアニリン、ポリピロール、PEDOT等の導電性高分子、金属粒子を用いた導電性インク等も使用可能である。
本発明のゲート絶縁膜の種類には特に限定はない。具体的には、ポリイミド、ポリビニルフェノール、ポリビニルアルコール、エポキシ等の絶縁ポリマーを塗布・焼成したり、CVDやスパッターによってSiO2やSiNx、酸化アルミニウム、酸化タンタル等を形成しても構わない。また、ゲート電極にタンタルやアルミニウムを用いている場合は、UV・オゾン処理や陽極酸化処理等によりゲート電極表面に形成される酸化タンタルや酸化アルミニウムを用いても良い。
図2に、本発明を用いたボトムコンタクト・ボトムゲート型電界効果トランジスタの概略断面図を示す。本発明を用いた電界効果トランジスタの構造としては他にも、ボトムコンタクト・トップゲート型、トップ・ボトムコンタクト型等が有る。また、ソース・ドレイン電極の上下にゲート電極を有するデュアルゲート型を用いても良い。
本発明の電界効果トランジスタは、電子デバイス、光電デバイスに利用することができる。好ましくは電子デバイスである。電子デバイスの具体例としては、表示素子、電子タグ、電磁波および圧力センサー等が挙げられる。
最後に、式(I)に示すような、加熱により逆ディールス・アルダー反応を起こす熱変換型のビシクロ構造を有したポルフィリン誘導体のクロロホルム溶液をスピンコートし、210℃、20分間の加熱により変換および結晶化させて、半導体層を形成した。
図4に、得られた電界効果トランジスタの断面SEM像を示す。観察倍率5万倍で測定したところ、テーパーの基板に対する角度は、1°であった。
結晶成長のビデオ観察において、ソース・ドレイン電極上、及びゲート絶縁膜上のどちらから結晶核が生成した場合でも、ソース・ドレイン電極とゲート絶縁膜間に跨って結晶成長が起こることが観測された。
得られた電界効果トランジスタは、13μmのチャネル長および500μmのチャネル幅において、5個のサンプルを測定したところ移動度は平均0.77cm2/V・sであり、また、移動度のばらつきは±10%であった。
図6に、得られた電界効果トランジスタの断面SEM像を示す。観察倍率5万倍で測定したところ、テーパーの基板に対する角度は、70°であった。
得られた電界効果トランジスタは、12μmのチャネル長および500μmのチャネル幅において、5個のサンプルを測定したところ平均0.70cm2/V・sの高い移動度が得られ、移動度のばらつきも±20%であった。
得られた電界効果トランジスタの断面SEM像を実施例1と同様に測定したところ、テーパーの基板に対する角度は、45°であった。
得られた電界効果トランジスタは、12μmのチャネル長および500μmのチャネル幅において、5個のサンプルを測定したところ移動度は平均0.92cm2/V・sであり、また、移動度のばらつきは±20%であった。
得られた電界効果トランジスタの断面SEM像を実施例1と同様に測定したところ、テーパーの基板に対する角度は、1°であった。
実施例2において、ポリメチルグルタルイミド(PMGI)レジストを用いずにネガ型のフォトレジスト(日本ゼオン社製ZPN-1150)のみを厚さ4μmにスピンコートした以外は、実施例2と同様にして電界効果トランジスタを作成した。
得られた電界効果トランジスタは、13μmのチャネル長および500μmのチャネル幅において、5個のサンプルを測定したところ移動度は平均0.28cm2/V・s、ばらつきは±40%であった。又、TEMの観察倍率10万倍で測定したところ、テーパーの基板に対する角度は、130°(逆テーパー)であった。
比較例1において、露光時間を15秒にした以外は、比較例1と同様にして電界効果トランジスタを作成した。得られた電界効果トランジスタは、10μmのチャネル長および500μmのチャネル幅において、5個のサンプルを測定したところ移動度は平均0.55cm2/V・s、ばらつきは±50%であった。又、テーパーの基板に対する角度は、90°であった。
比較例1において、熱変換型のビシクロポルフィリンに変えて、ペンタセンを50nmの膜厚になるように、1Å/sの速度で真空蒸着によって製膜し、半導体層を形成した他は、比較例1と同様にして電界効果トランジスタを作成した。テーパーの基板に対する角度は130°(逆テーパー)であった。得られた電界効果トランジスタは、13μmのチャネル長および500μmのチャネル幅において、3個のサンプルを測定したところ移動度は平均0.0088cm2/V・sであった。
比較例2において、熱変換型のビシクロポルフィリンに変えて、ペンタセンを真空蒸着によって製膜し、半導体層を形成した他は、比較例2と同様にして電界効果トランジスタを作成した。テーパーの基板に対する角度は90°であった。得られた電界効果トランジスタは、10μmのチャネル長および500μmのチャネル幅において、3個のサンプルを測定したところ移動度は平均0.014cm2/V・sであった。
実施例2において、熱変換型のビシクロポルフィリンに変えて、ペンタセンを真空蒸着によって製膜し、半導体層を形成した他は、実施例2と同様にして電界効果トランジスタを作成した。テーパーの基板に対する角度は70°であった。得られた電界効果トランジスタは、13μmのチャネル長および500μmのチャネル幅において、3個のサンプルを測定したところ移動度は平均0.0028cm2/V・sであった。
実施例3において、熱変換型のビシクロポルフィリンに変えて、ペンタセンを真空蒸着によって製膜し、半導体層を形成した他は、実施例3と同様にして電界効果トランジスタを作成した。テーパーの基板に対する角度は45°であった。得られた電界効果トランジスタは、12μmのチャネル長および500μmのチャネル幅において、3個のサンプルを測定したところ移動度は平均0.0070cm2/V・sであった。
本発明の電界効果トランジスタはフラットパネルディスプレイ、フレキシブルディスプレイ、電子タグ、光・圧力センサー等の種々の電子デバイスに利用可能である。
2 ゲート絶縁膜
3 ゲート電極
4 半導体層
Claims (9)
- 少なくとも基板、塗布法によって形成される半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタであって、チャネル長方向に平行でかつ基板に対して垂直な断面において、ソース電極及び/又はドレイン電極がテーパーを有し、該テーパーの前記基板に対する角度が70°以下であることを特徴とする電界効果トランジスタ。
- 半導体がアヌレン構造の有機半導体である請求項1に記載の電界効果トランジスタ。
- 移動度のばらつきが±30%以下である請求項1又は2記載の電界効果トランジスタ。
- 少なくとも基板、半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタの製造方法であって、チャネル長方向に平行でかつ基板に対して垂直な断面においてソース電極及び/又はドレイン電極がテーパーを有するように、ソース電極及び/又はドレイン電極を形成する工程、並びに、半導体を含有する塗布液を塗布する工程を含む電界効果トランジスタの製造方法。
- 少なくとも基板、半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタの製造方法であって、チャネル長方向に平行でかつ基板に対して垂直な断面においてソース電極及び/又はドレイン電極がテーパーを有するように、ソース電極及び/又はドレイン電極を形成する工程、半導体の前駆体を含有する塗布液を塗布する工程、並びに、加熱及び/又は光照射により該前駆体を半導体に変換する工程を含む電界効果トランジスタの製造方法。
- テーパーを有するソース電極及び/又はドレイン電極の形成を、フォトレジスト層を二段形成して露光し非硬化部分を除去し、金属層を形成した後リフトオフ法により不要な金属層を除去することにより行うことを特徴とする請求項4又は5記載の電界効果トランジスタの製造方法。
- 請求項4~6のいずれか一項に記載の方法により製造された電界効果トランジスタ。
- 少なくとも基板、塗布法によって形成される半導体層、ソース電極及びドレイン電極を有する電界効果トランジスタを製造するにあたり、チャネル長方向に平行でかつ基板に対して垂直な断面においてソース電極及び/又はドレイン電極がテーパーを有するように、ソース電極及び/又はドレイン電極を形成することにより、電界効果トランジスタの移動度を向上させる方法。
- 請求項1~3及び7のいずれか一項に記載の電界効果トランジスタを用いた電子デバイス。
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CN201080014681.7A CN102379042B (zh) | 2009-04-10 | 2010-04-07 | 场效应晶体管、其制造方法以及使用了该场效应晶体管的电子器件 |
EP10761720.1A EP2418684A4 (en) | 2009-04-10 | 2010-04-07 | FIELD EFFECT TRANSISTOR, MANUFACTURING METHOD THEREFOR, AND ELECTRONIC DEVICE USING THE SAME |
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JP2016082154A (ja) * | 2014-10-21 | 2016-05-16 | 凸版印刷株式会社 | 有機半導体薄膜トランジスタ素子、有機半導体薄膜トランジスタ素子のソース電極とドレイン電極の製造方法および有機半導体薄膜トランジスタ素子の製造方法 |
JP2018156963A (ja) * | 2017-03-15 | 2018-10-04 | 株式会社リコー | 電界効果型トランジスタ、表示素子、表示装置、システム、及びそれらの製造方法 |
JP2020098880A (ja) * | 2018-12-19 | 2020-06-25 | 凸版印刷株式会社 | 有機薄膜トランジスタおよび電子装置 |
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CN102379042B (zh) | 2015-04-29 |
US20120086008A1 (en) | 2012-04-12 |
JPWO2010117021A1 (ja) | 2012-10-18 |
EP2418684A1 (en) | 2012-02-15 |
TW201103149A (en) | 2011-01-16 |
US8969871B2 (en) | 2015-03-03 |
CN102379042A (zh) | 2012-03-14 |
EP2418684A4 (en) | 2016-12-14 |
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KR20110138343A (ko) | 2011-12-27 |
TWI514570B (zh) | 2015-12-21 |
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