WO2014192701A1 - Dispositif à semi-conducteur et procédé de fabrication d'un dispositif à semi-conducteur - Google Patents

Dispositif à semi-conducteur et procédé de fabrication d'un dispositif à semi-conducteur Download PDF

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WO2014192701A1
WO2014192701A1 PCT/JP2014/063873 JP2014063873W WO2014192701A1 WO 2014192701 A1 WO2014192701 A1 WO 2014192701A1 JP 2014063873 W JP2014063873 W JP 2014063873W WO 2014192701 A1 WO2014192701 A1 WO 2014192701A1
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thin film
electride
semiconductor layer
semiconductor device
source electrode
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English (en)
Japanese (ja)
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俊成 渡邉
宮川　直通
伊藤　和弘
暁 渡邉
光井　彰
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3457—Sputtering using other particles than noble gas ions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • H01L29/78618—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure
    • 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
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • 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
    • 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]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single 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 semiconductor device and a method for manufacturing the semiconductor device.
  • a semiconductor device such as a thin film transistor constructed by forming electrodes such as a source, a drain, and a gate, and a semiconductor layer on an insulating substrate has attracted attention (for example, Patent Document 1).
  • Such a semiconductor device can be applied to various electronic devices such as an electro-optical device, for example.
  • the present invention has been made in view of such a background, and an object of the present invention is to provide a semiconductor device with higher performance and higher functionality than conventional ones. Another object of the present invention is to provide a method for manufacturing such a semiconductor device.
  • a semiconductor device having a source electrode, a drain electrode, a gate electrode and a semiconductor layer
  • a semiconductor device comprising an amorphous oxide electride thin film containing calcium atoms and aluminum atoms between one or both of the source electrode and the drain electrode and the semiconductor layer.
  • the molar ratio (Ca / Al) of aluminum atoms to calcium atoms in the electride thin film may be in the range of 0.3 to 5.0.
  • the electride thin film may have an electron density of 2.0 ⁇ 10 17 cm ⁇ 3 or more.
  • the electride thin film may have a thickness of 100 nm or less.
  • the semiconductor layer may include an oxide semiconductor or an organic semiconductor.
  • the semiconductor layer may be disposed between the source electrode and the gate electrode, or the semiconductor layer may be disposed on a side farther from the gate electrode than the source electrode. .
  • a method of manufacturing a semiconductor device having a source electrode, a drain electrode, a gate electrode, and a semiconductor layer, (1) forming a thin film of an amorphous oxide electride containing calcium atoms and aluminum atoms between one or both of the source electrode and the drain electrode and the semiconductor layer; A method of manufacturing a semiconductor device is provided.
  • the manufacturing method according to the present invention further includes: (A) forming a semiconductor layer on the substrate; (B) forming a source electrode and a drain electrode; (C) forming a gate electrode; Have The step (1) may be performed between the step (a) and the step (b).
  • the manufacturing method according to the present invention further includes: (A) forming a source electrode and a drain electrode on a substrate; (B) forming a semiconductor layer; (C) forming a gate electrode; Have The step (1) may be performed between the step (a) and the step (b).
  • the manufacturing method according to the present invention further includes: (A) forming a gate electrode on the substrate; (B) forming a semiconductor layer; (C) forming a source electrode and a drain electrode; Have The step (1) may be performed between the step (b) and the step (c).
  • the manufacturing method according to the present invention further includes: (A) forming a gate electrode on the substrate; (B) forming a source electrode and a drain electrode; (C) forming a semiconductor layer; Have The step (1) may be performed between the step (b) and the step (c).
  • the molar ratio (Ca / Al) of aluminum atoms to calcium atoms in the electride thin film may be in the range of 0.3 to 5.0.
  • the electride thin film may have an electron density of 2.0 ⁇ 10 17 cm ⁇ 3 or more.
  • the electride thin film may have a thickness of 100 nm or less.
  • the semiconductor layer may include an oxide semiconductor or an organic semiconductor.
  • amorphous oxide electride containing calcium atom and aluminum atom is also simply referred to as “amorphous oxide electride”, and “amorphous oxidation containing calcium atom and aluminum atom”.
  • the “electride thin film” is also simply referred to as “electride thin film”.
  • the present invention it is possible to provide a semiconductor device with higher performance and higher functionality than conventional ones.
  • the present invention can also provide a method for manufacturing such a semiconductor device.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of a semiconductor device according to an embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing an example of a semiconductor device according to the present invention configured by a top gate structure-bottom contact method.
  • 1 is a cross-sectional view schematically showing an example of a semiconductor device according to the present invention configured by a bottom gate structure-top contact method.
  • 1 is a cross-sectional view schematically showing an example of a semiconductor device according to the present invention configured by a bottom gate structure-bottom contact method.
  • FIG. It is the figure which showed typically an example of the flow at the time of manufacturing the semiconductor device by one Example of this invention.
  • FIG. 1 shows a schematic cross section of a conventional semiconductor device.
  • the conventional semiconductor device 1 includes a substrate 10, a semiconductor layer 5, a source electrode 20, a drain electrode 22, and a gate electrode 24.
  • the semiconductor layer 5 is disposed on the substrate 10, and the source electrode 20 and the drain electrode 22 are disposed on the semiconductor layer 5.
  • a gate electrode 24 is disposed on the source electrode 20 and the drain electrode 22 with a gate insulating layer 30 interposed therebetween.
  • the semiconductor layer 5 a layer made of an oxide semiconductor, a layer made of an organic compound semiconductor, or the like is used.
  • Such a semiconductor device 1 can be used for, for example, an electro-optical device such as a liquid crystal panel or electronic paper, and a light-emitting display device.
  • the conventional semiconductor device 1 is required to reduce the contact resistance at the interface between the source electrode 20 and the semiconductor layer 5 and at the interface between the drain electrode 22 and the semiconductor layer 5 in order to achieve higher performance and higher functionality. ing. This is because if the contact resistance at this interface increases, the operating characteristics of the semiconductor device 1 deteriorate.
  • the semiconductor layer 5 is an N-type semiconductor
  • the ohmic junction means a state in which a metal and a semiconductor are bonded so that a space charge layer is not formed on the semiconductor layer side, and in this case, no rectification occurs at the metal / semiconductor interface (that is, electrons are not Flows in both directions).
  • the work function of the source electrode 20 / drain electrode 22 is set to the work function of the semiconductor layer 5. It needs to be smaller than the function. However, there are usually not many metal materials having such a work function. In addition, a metal having a low work function is active and highly reactive, and a reaction layer is easily formed with other components. Therefore, it is difficult to directly bond a metal having a low work function and a semiconductor layer. For this reason, such a problem causes a problem that the material of the source electrode 20 / drain electrode 22 is largely limited.
  • a semiconductor device having a source electrode, a drain electrode, a gate electrode, and a semiconductor layer
  • a semiconductor device comprising an amorphous oxide electride thin film containing calcium atoms and aluminum atoms between one or both of the source electrode and the drain electrode and the semiconductor layer.
  • the semiconductor device according to the present invention is characterized in that a thin film of an amorphous oxide electride containing calcium atoms and aluminum atoms is disposed between one or both of the source electrode and the drain electrode and the semiconductor layer.
  • the amorphous oxide electride thin film containing calcium atoms and aluminum atoms has semiconducting electrical characteristics and a relatively low work function.
  • the work function of this thin film is in the range of 2.4 eV to 4.5 eV (eg, 2.8 eV to 3.2 eV).
  • this thin film has a feature of high electron density.
  • the electron density of the thin film is, for example, in the range of 2.0 ⁇ 10 17 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the presence of such a thin film can significantly reduce the contact resistance between one or both of the source electrode and the drain electrode and the semiconductor layer. Therefore, the present invention can provide a semiconductor device having higher operating characteristics than conventional ones.
  • the present invention is more effective when the semiconductor layer is an N-type semiconductor. This is particularly effective when the work function of the source electrode and the work function of the drain electrode are larger than the work function of the semiconductor layer.
  • an ohmic junction can be developed by lowering the work functions of the source electrode and the drain electrode than the semiconductor layer.
  • a metal having a low work function is active and highly reactive, and easily forms a reaction layer with other components, so that it is difficult to develop an ohmic junction.
  • the electride thin film according to the present invention has a low work function, it has a high chemical durability and a higher carrier density (electron density). Therefore, an ohmic junction can be developed between the semiconductor layer (N-type semiconductor) and the electride thin film, and a tunnel effect can be developed between the source electrode and the drain electrode (metal). As a result, the contact resistance between one or both of the source electrode and the drain electrode and the semiconductor layer can be significantly reduced, and a high-performance semiconductor device can be provided as compared with the related art.
  • the work function of the electride thin film is preferably smaller than the work function of the semiconductor layer.
  • the difference between the work function of the semiconductor layer and the work function of the electride thin film is preferably greater than 0 to 3.0 eV, more preferably 0.1 eV to 2.5 eV, and even more preferably 0.5 eV to 2.0 eV.
  • the present invention is more effective when the semiconductor layer is an oxide semiconductor, and particularly effective when the semiconductor layer is an N-type oxide semiconductor.
  • a layer formed of IGZO (In—Ga—Zn—O) which is an example of an oxide semiconductor is used as the semiconductor layer.
  • the work function of the layer made of IGZO is 4.3 eV to 4.5 eV.
  • Al aluminum
  • the work function of the source and drain electrodes made of Al is 4.1 eV. In this case, when one or both of the source electrode and the drain electrode and the semiconductor layer are directly bonded, a reaction layer is generated and the ohmic junction is hardly developed.
  • an amorphous oxide electride thin film containing calcium atoms and aluminum atoms is disposed between one or both of the source electrode and the drain electrode and the semiconductor layer.
  • the work function of this electride thin film is in the range of 2.4 eV to 4.5 eV, for example, can be in the range of 2.8 eV to 3.2 eV, which is sufficient compared with the work function of the layer made of IGZO. Can be lowered.
  • this electride thin film is chemically stable, it is difficult to form a reaction layer.
  • the electron resistance of the thin film of electride is high, so that the contact resistance is reduced by the tunnel effect. For this reason, it becomes easy to develop an ohmic junction, and the contact resistance between one or both of the source electrode and the drain electrode and the semiconductor layer can be reduced. As a result, a semiconductor device with higher performance than before can be provided.
  • a layer made of an organic semiconductor generally has a carrier density as low as 10 10 cm ⁇ 1 to less than 10 17 cm ⁇ 1, and easily generates contact resistance with a metal source electrode and drain electrode.
  • the carrier type is known to be affected by the relative relationship between the HOMO and LUMO of the layer made of organic semiconductor and the work function of the source electrode and the drain electrode.
  • the former is smaller than the latter, and the former is larger than the latter.
  • a layer made of C60 fullerene which is an example of an organic semiconductor, is applied as the semiconductor layer.
  • the work function of C60 fullerene is 4.6 eV.
  • gold (Au) is applied as the source and drain electrodes
  • the work function of the source and drain electrodes made of Au is 5.0 eV.
  • an amorphous oxide electride thin film containing calcium atoms and aluminum atoms is disposed between one or both of the source electrode and the drain electrode and the semiconductor layer.
  • the work function of this electride thin film is in the range of 2.4 eV to 4.5 eV, for example, in the range of 2.8 eV to 3.2 eV, compared with the work function of the layer made of C60 fullerene. It can be made sufficiently low. Moreover, since this electride thin film is chemically stable, it is difficult to form a reaction layer. In addition, at the interface between the source electrode and drain electrode (metal) and the thin film of electride, the electron resistance of the thin film of electride is high, so that the contact resistance is reduced by the tunnel effect. For this reason, it becomes easy to develop an ohmic junction, and the contact resistance between one or both of the source electrode and the drain electrode and the semiconductor layer can be reduced. As a result, a semiconductor device with higher performance than before can be provided.
  • the difference between ⁇ F and ⁇ B is preferably close to zero.
  • the absolute value of the difference between ⁇ F and ⁇ B is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.
  • a layer made of IGZO which is an example of an oxide semiconductor
  • ⁇ F is 0.5 eV
  • ⁇ B is 0.1 eV to 0.3 eV.
  • the difference between ⁇ F and ⁇ B is 0.4 or less, and a very low contact resistance can be achieved.
  • the electride thin film may have a high ionization potential.
  • the ionization potential of the electride thin film may be 7.0 eV to 9.0 eV, or 7.5 eV to 8.5 eV.
  • the semiconductor layer is an organic semiconductor
  • the ionization potential of the electride thin film is larger than the ionization potential of the layer made of the organic semiconductor.
  • the difference in ionization potential between the electride thin film and the organic semiconductor layer may be 1.1 eV to 3.5 eV, 1.3 eV to 3.3 eV, or 1.6 eV to 3.0 eV. It may be.
  • the difference between the ionization potential and work function of the thin film of electride is larger than the difference between the ionization potential and work function of the layer made of the organic semiconductor.
  • ⁇ E is the difference (IP ⁇ WF) between the ionization potential (IP) and work function (WF) of the electride thin film.
  • a difference between an ionization potential (IP) and a work function (WF) of a layer made of an organic semiconductor is represented by ⁇ A.
  • the difference ( ⁇ E ⁇ A) between the two is preferably 1.3 eV to 5.8 eV, more preferably 2.0 eV to 5.0 eV, and particularly preferably 2.5 eV to 4.5 eV.
  • the electride thin film has a high ionization potential, and the ionization potential is sufficiently large compared to the layer made of an organic semiconductor.
  • the difference between the ionization potential and the work function is sufficiently large for the layer made of an organic semiconductor. If it is too large, an excellent hole blocking effect can be obtained. This is because the difference ( ⁇ E ⁇ A) between the ionization potential difference ( ⁇ E) of the above-described electride thin film and the difference between the ionization potential of the organic semiconductor layer and the work function ( ⁇ A) is the energy in hole conduction. It becomes a barrier.
  • an electride of an amorphous oxide containing calcium atoms and aluminum atoms refers to an amorphous composed of calcium atoms, aluminum atoms, and oxygen atoms. It means an amorphous solid substance composed of a solvate having a solvent and electrons as a solute. Electrons in the amorphous oxide act as anions. The electrons may exist as bipolarons.
  • FIG. 2 conceptually shows the structure of the amorphous oxide electride.
  • the amorphous oxide electride 70 has a characteristic partial structure called a bipolaron 74 in an amorphous solvent 72 composed of calcium atoms, aluminum atoms and oxygen atoms. Exist in a distributed state.
  • the bipolarron 74 is configured such that two cages 76 are adjacent to each other, and each cage 76 includes an electron (solute) 78.
  • the state of the amorphous oxide is not limited to the above, and two electrons (solutes) 78 may be included in one cage 76.
  • a plurality of these cages may be aggregated, and the aggregated cage can be regarded as a microcrystal. Therefore, a state in which the microcrystal is included in the amorphous is also regarded as amorphous in the present invention.
  • the amorphous oxide electride is Sr, Mg, Ba, Si, Ge, Ga, in addition to calcium atom, aluminum atom, and oxygen atom within the range in which the cage structure of bipolaron is maintained.
  • One or more atoms selected from the group consisting of In and B may be included.
  • the amorphous oxide electride may be a compound in which two electrons included in two cages are replaced with other anions.
  • Other anions include, for example, one or more selected from the group consisting of H ⁇ , H 2 ⁇ , H 2 ⁇ , O ⁇ , O 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , and S 2 ⁇ .
  • Anions may be mentioned.
  • the amorphous oxide electride exhibits semiconducting electrical characteristics and has a low work function.
  • the work function may be 2.4 eV to 4.5 eV, and preferably 2.8 eV to 3.2 eV.
  • An amorphous oxide electride has a high ionization potential.
  • the ionization potential may be 7.0 eV to 9.0 eV, or 7.5 eV to 8.5 eV.
  • the electride thin film according to the present invention is transparent in visible light. Further, by measuring the light absorption characteristics of the thin film sample and measuring the light absorption coefficient in the vicinity of 4.6 eV, whether or not bipolaron is present in the thin film sample, that is, the thin film sample is an amorphous oxide electride. Can be confirmed.
  • the molar ratio (Ca / Al) of aluminum atoms to calcium atoms in the electride thin film is preferably in the range of 0.3 to 5.0.
  • a high electron density can be maintained.
  • it is excellent in the durability of a thin film as it is 5.0 or less.
  • a range of 0.5 to 1.6 is more preferable, and a range of 0.55 to 1.00 is particularly preferable.
  • the composition analysis of the thin film can be performed by XPS method, EPMA method, EDX method or the like. Analysis by the XPS method is possible when the film thickness is 100 nm or less, EPMA method when the film thickness is 50 nm or more, and EDX method when it is 3 ⁇ m or more.
  • the electride thin film of the present invention when X-ray diffraction is measured, no peak is observed and only a halo is observed.
  • the electride thin film may contain microcrystals. Whether or not microcrystals are contained in the thin film is determined from, for example, a cross-sectional TEM (transmission electron microscope) photograph of the thin film.
  • the composition in the crystalline state is represented by 12CaO ⁇ 7Al 2 O 3 , CaO ⁇ Al 2 O 3 , 3CaO ⁇ Al 2 O 3 and the like.
  • the light absorption coefficient at the position of 4.6 eV may be 100 cm ⁇ 1 or more, 200 cm ⁇ 1 or more, or 1000 cm ⁇ 1 or more. is good, may be at 5000 cm -1 or more may also be 8000 cm -1 or more, it may be 10000 cm -1 or higher.
  • the absorption coefficient at a position of 4.6 eV can be measured with high accuracy when a thin film having a thickness of 50 nm or more, preferably a thin film having a thickness of 100 nm or more is used.
  • the electride thin film preferably contains electrons in an electron density range of 2.0 ⁇ 10 17 cm ⁇ 3 or more and 2.3 ⁇ 10 21 cm ⁇ 3 or less.
  • the electron density is more preferably 1.0 ⁇ 10 18 cm ⁇ 3 or more, further preferably 1 ⁇ 10 19 cm ⁇ 3 or more, and particularly preferably 1 ⁇ 10 20 cm ⁇ 3 or more.
  • the electron density of the electride thin film can be measured by an iodometric titration method.
  • the density of bipolarons in the electride thin film can be calculated by multiplying the measured electron density by 1/2.
  • iodine titration method a sample of an electride thin film is immersed in a 5 mol / l iodine aqueous solution, dissolved by adding hydrochloric acid, and then the amount of unreacted iodine contained in this solution is adjusted with sodium thiosulfate. This is a method for titration detection.
  • the thickness of the electride thin film is not limited to this, but may be, for example, 100 nm or less, preferably 10 nm or less, and more preferably 5 nm or less. It may be 0.5 nm or more.
  • the thin film of electride has conductivity due to hopping conduction of electrons in the cage.
  • the direct current conductivity at room temperature of the thin film of electride according to the present invention may be 10 ⁇ 11 S ⁇ cm ⁇ 1 to 10 ⁇ 1 S ⁇ cm ⁇ 1 , and 10 ⁇ 7 S ⁇ cm ⁇ 1. It may be ⁇ 10 ⁇ 3 S ⁇ cm ⁇ 1 .
  • the electride thin film may have an F + center in which one electron is captured in an oxygen vacancy as a partial structure.
  • the F + center is configured by a plurality of Ca 2+ ions surrounded by one electron and does not have a cage.
  • the F + center has light absorption in the visible light range of 1.55 eV to 3.10 eV centered on 3.3 eV.
  • the concentration of F + center is less than 5 ⁇ 10 18 cm ⁇ 3 , the transparency of the thin film is increased, which is preferable.
  • the concentration of the F + center is more preferably 1 ⁇ 10 18 cm ⁇ 3 or less, and further preferably 1 ⁇ 10 17 cm ⁇ 3 or less. Note that the concentration of the F + center can be measured by a signal intensity having a g value of 1.998 in ESR.
  • the ratio of the light absorption coefficient at a position of 3.3 eV to the light absorption coefficient at a photon energy position of 4.6 eV may be 0.35 or less, more preferably 0.25 or less. 0.15 or less is more preferable.
  • the thin film of electride is excellent in flatness because it does not have a crystal grain boundary as compared with the polycrystalline thin film.
  • the root mean square roughness (RMS) of the surface of the electride thin film according to the present invention may be 0.1 nm to 10 nm, or may be 0.2 nm to 5 nm. It is more preferable that the RMS is 2 nm or less because the characteristics of the device are improved. Further, if the RMS is 10 nm or more, the characteristics of the element may be deteriorated, so that a polishing step or the like needs to be added.
  • the RMS can be measured using, for example, an atomic force microscope.
  • the composition of the electride thin film may be different from the stoichiometric ratio of 12CaO ⁇ 7Al 2 O 3 , or may be different from the composition ratio of the target used in the production.
  • FIG. 3 schematically shows a cross section of a semiconductor device (first semiconductor device) 100 according to an embodiment of the present invention.
  • the first semiconductor device 100 includes a substrate 110, a semiconductor layer 105, a source electrode 120, a drain electrode 122, and a gate electrode 124.
  • the semiconductor layer 105 is disposed on the substrate 110, and the source electrode 120 and the drain electrode 122 are disposed on the semiconductor layer 105.
  • a gate electrode 124 is disposed on the source electrode 120 and the drain electrode 122 with a gate insulating layer 130 interposed therebetween.
  • the first semiconductor device 100 includes an amorphous oxide electride containing calcium atoms and aluminum atoms between the source electrode 120 and the semiconductor layer 105 and / or between the drain electrode 122 and the semiconductor layer 105.
  • the thin film (electride thin film) 150 is arranged.
  • the first electride thin film 150 a is disposed between the source electrode 120 and the semiconductor layer 105
  • the second electride thin film 150 b is disposed between the drain electrode 122 and the semiconductor layer 105. Is arranged.
  • the electride thin films 150a and 150b are characterized by a small work function and a high electron density.
  • the contact resistance at the interface between the source electrode 120 and the semiconductor layer 105 can be significantly suppressed. It is done.
  • the second electride thin film 150 b is disposed between the drain electrode 122 and the semiconductor layer 105, the contact resistance at the interface between the drain electrode 122 and the semiconductor layer 105 can be significantly suppressed.
  • the first semiconductor device 100 can exhibit significantly higher operation characteristics than the conventional one.
  • the material of the substrate 110 is not particularly limited.
  • the substrate 110 may be an insulating substrate such as a glass substrate, a ceramic substrate, a plastic substrate, and a resin substrate.
  • the substrate 110 is a semiconductor substrate or a metal substrate, and an insulating layer may be formed on the surface.
  • the material of the semiconductor layer 105 is not particularly limited.
  • the semiconductor layer 105 may be made of a general semiconductor material such as an oxide semiconductor and an organic semiconductor.
  • oxide semiconductor examples include oxides of transition metals such as In, Ti, Nb, Sn, Zn, Gd, Cd, Zr, Y, La, and Ta, SrTiO 3 , CaTiO 3 , ZnO ⁇ Rh 2 O 3. , CuGaO 2 , and oxides such as SrCu 2 O 2 .
  • the oxide semiconductor may include at least one oxide of In, Sn, Zn, Ga, and Cd.
  • the oxide semiconductor preferably includes at least one oxide of In, Sn, Zn, and Ga, and includes an oxide including at least one of In, Ga, and Zn (eg, an In—O-based oxide). ) Is more preferable.
  • the oxide semiconductor may include at least two of In, Ga, and Zn, for example, all oxides.
  • oxide semiconductors examples include IGZO (In—Ga—Zn—O), ITO (In—Sn—O), ISZO (In—Si—Zn—O), IGO (In—Ga—O), ITZO (In—Sn—Zn—O), IZO (In—Zn—O), IHZO (In—Hf—Zn—O), and the like.
  • a film formed using such an oxide semiconductor may be amorphous, crystalline, or in a state containing amorphous and crystalline.
  • organic semiconductors include polycyclic aromatic compounds, conjugated double bond compounds, macrocyclic compounds, metal phthalocyanine complexes, charge transfer complexes, condensed ring tetracarboxylic acid diimides, oligothiophenes, fullerenes, and carbon nanotubes. , Etc.
  • pentacene pentacene
  • tetracene ⁇ -sexithiophene (6T)
  • copper phthalocyanine bis (1,2,5-thiadiazolo) -p-quinobis (1)
  • PTV poly (2,5-thienylenevinylene)
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • F8T2 poly [(9,9 -Dioctylfluorenyl-2,7-diyl) -co-bithiophene]
  • TCNQ 7,7,8,8, -tetracyanoquinodimethane
  • PTCDA perylene-3,4,9,10-tetracarboxylic dianhydride
  • NTCDA 1,4,5,8-naphthalenetetracarboxylic dianhydride
  • PTCDI-C8H N-dioctyl-3,4,9,10-perylenetetracarboxylic acid diimide
  • F16CuPc 3 ′, 4′-dibutyl-5,5 ′′ -bis (dicyanomethylene) -5,5 ′′ -dihydro-2,2
  • the material of the source electrode 120 and the drain electrode 122 is not particularly limited as long as it has conductivity.
  • the source electrode 120 and the drain electrode 122 may be made of metal, for example.
  • the source electrode 120 and the drain electrode 122 may be an alloy containing at least one element selected from Al, Ag, Au, Cr, Cu, Ta, Ti, Mo, and W, for example.
  • the source electrode 120 and the drain electrode 122 are made of, for example, ITO, antimony oxide (Sb 2 O 3 ), zirconium oxide (ZrO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), or IZO (Indium Zinc).
  • the source electrode 120 and the drain electrode 122 may be transparent electrodes using a metal that is thin enough to transmit visible light.
  • the source electrode 120 and the drain electrode 122 are formed of metals such as platinum, gold, aluminum, chromium, nickel, cobalt, copper, titanium, magnesium, calcium, barium, and sodium, and the like. You may comprise with the alloy containing.
  • the work function of the semiconductor layer 105 may be 3.5 eV to 7.0 eV, and is preferably 4.0 eV to 5.0 eV.
  • the semiconductor layer 105 may have a carrier density of 10 11 cm ⁇ 3 to less than 10 17 cm ⁇ 3 , and preferably 10 14 cm ⁇ 3 to 10 16 cm ⁇ 3 .
  • Gate electrode 1234 The material of the gate electrode 124 is not particularly limited as long as it has conductivity.
  • the gate electrode 124 is, for example, an element selected from Al, Ag, Au, Cr, Cu, Ta, Ti, Mo, and W, or a metal or alloy containing these elements as a component, or an alloy that combines the above-described elements Etc.
  • the gate electrode 124 is made of, for example, ITO, antimony oxide (Sb 2 O 3 ), zirconium oxide (ZrO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), IZO (Indium Zinc Oxide), or AZO.
  • the gate electrode 124 may be a transparent electrode using a metal thin enough to transmit visible light.
  • the gate insulating layer 130 may be made of an inorganic insulating material such as silicon oxide, silicon nitride, silicon oxide containing nitrogen and silicon nitride containing oxygen, or an organic insulating material such as acrylic or polyimide.
  • the gate insulating layer 130 has a skeleton structure formed of a bond of silicon and oxygen, and has an organic group (for example, an alkyl group or an aryl group) containing at least hydrogen as a substituent and a fluoro group, a so-called siloxane-based material. It may be constituted by.
  • the gate insulating layer 130 may be a single layer or may be composed of two or more layers.
  • the first semiconductor device 100 shown in FIG. 3 has a so-called top gate structure-top contact method.
  • the arrangement structure of each member constituting the semiconductor device is not limited to this.
  • top gate structure-top contact system (i) top gate structure-bottom contact system, (iii) bottom gate structure-top contact system, and (Iii) There is a bottom gate structure-bottom contact method, and the like.
  • FIG. 3 described above shows an example of the semiconductor device 100 configured by the top gate structure-top contact method.
  • the gate electrode 124 is disposed on the semiconductor layer 105 (top gate structure), and the source electrode 120 and the drain electrode 122 are also disposed on the semiconductor layer 105. (Top contact method). Note that in the semiconductor device 100, the semiconductor layer 105 may be a channel etch type or a channel protection type.
  • FIG. 4 shows an example of a semiconductor device configured by a top gate structure-bottom contact method.
  • this semiconductor device 400 includes a semiconductor layer 405 formed on a substrate 410, a source electrode 420 and a drain electrode 422, a gate insulating layer 430, and a gate electrode 424.
  • the gate electrode 424 is disposed on the semiconductor layer 405 (top gate structure).
  • the source electrode 420 and the drain electrode 422 are disposed below the semiconductor layer 405 (bottom contact method).
  • the first electride thin film 450 a is disposed between the source electrode 420 and the semiconductor layer 405, and the first electride thin film 450 a is disposed between the drain electrode 422 and the semiconductor layer 405.
  • An electride thin film 450b is disposed. However, one of the first electride thin film 450a and the second electride thin film 450b may be omitted.
  • FIG. 5 shows an example of a semiconductor device configured by a bottom gate structure-top contact method.
  • the semiconductor device 500 includes a semiconductor layer 505, a source electrode 520 and a drain electrode 522, a gate insulating layer 530, and a gate electrode 524 on a substrate 510.
  • the gate electrode 524 is disposed below the semiconductor layer 505 (bottom gate structure).
  • the source electrode 520 and the drain electrode 522 are disposed above the semiconductor layer 505 (top contact method).
  • the semiconductor layer 505 may be a channel etch type or a channel protection type.
  • the first electride thin film 550 a is disposed between the source electrode 520 and the semiconductor layer 505, and the first electrode thin film 550 a is disposed between the drain electrode 522 and the semiconductor layer 505. 2 electride thin film 550b is disposed. However, one of the first electride thin film 550a and the second electride thin film 550b may be omitted.
  • FIG. 6 shows an example of a semiconductor device configured by a bottom gate structure-bottom contact method.
  • the semiconductor device 600 includes a semiconductor layer 605, a source electrode 620 and a drain electrode 622, a gate insulating layer 630, and a gate electrode 624 on a substrate 610.
  • the gate electrode 624 is disposed below the semiconductor layer 605 (bottom gate structure).
  • the source electrode 620 and the drain electrode 622 are also disposed below the semiconductor layer 605 (bottom contact method).
  • a first electride thin film 650 a is disposed between the source electrode 620 and the semiconductor layer 605, and the second electrode 622 and the semiconductor layer 605 are disposed between the second electrode 622 and the semiconductor layer 605.
  • An electride thin film 650b is disposed. However, one of the first electride thin film 650a and the second electride thin film 650b may be omitted.
  • the semiconductor device in the present invention may be configured in any of these modes.
  • the semiconductor device according to the present invention has an effect that the contact resistance can be significantly suppressed at the interface between the source electrode and the semiconductor layer and / or the interface between the drain electrode and the semiconductor layer. It will be clear.
  • the type of the semiconductor device is not particularly limited.
  • the semiconductor device may be, for example, a field effect transistor such as a thin film transistor as shown in FIGS.
  • a bottom contact type configuration is preferable. The deterioration of the organic semiconductor due to the manufacturing process can be further prevented.
  • FIG. 7 schematically shows an example of a flow for manufacturing the first semiconductor device.
  • Forming a semiconductor layer on the substrate step S110; Forming a thin film of an amorphous oxide electride containing calcium atoms and aluminum atoms (step S120); Forming a source electrode and a drain electrode (step S130); Forming a gate electrode (step S140); Have
  • Step S110 First, the semiconductor layer 105 is formed over the substrate 110.
  • the method for forming the semiconductor layer 105 is not particularly limited, and the semiconductor layer 105 may be formed on the substrate 110 by a conventionally performed method.
  • the semiconductor layer 105 is formed over the substrate 110 by a general sputtering method or the like.
  • the semiconductor layer 105 is formed over the substrate 110 by an evaporation method, a spin coating method, a droplet discharge method, or the like.
  • the deposited semiconductor layer 105 is patterned into a desired pattern.
  • the semiconductor layer 105 can be patterned into a desired pattern by performing photolithography or the like.
  • the pattern of the semiconductor layer 105 can be directly formed by a droplet discharge method or the like.
  • Step S120 Next, an electride thin film is formed on the semiconductor layer 105.
  • This thin film of electride later becomes the thin film 150a of the first electride and / or the thin film 150b of the second electride.
  • a method of forming a thin film of electride Preparing a target of crystalline C12A7 electride having an electron density of 2.0 ⁇ 10 17 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 (S121); A step of forming a film on the semiconductor layer by a vapor deposition method in an atmosphere having an oxygen partial pressure of less than 0.1 Pa using the target (S122); A film forming method having the above will be described.
  • Step S121 First, a deposition target used in the subsequent step S120 is prepared.
  • the target is composed of crystalline C12A7 electride.
  • Crystal C12A7 means a crystal of 12CaO ⁇ 7Al 2 O 3 and an isomorphous compound having a crystal structure equivalent to this.
  • the mineral name of this compound is “mayenite”.
  • the crystalline C12A7 in the present invention is a compound in which some or all of Ca atoms and / or Al atoms in the C12A7 crystal skeleton are substituted with other atoms within a range in which the cage structure formed by the skeleton of the crystal lattice is maintained.
  • the same type compound may be used in which some or all of the free oxygen ions in the cage are replaced with other anions.
  • C12A7 is sometimes denoted as Ca 12 Al 14 O 33 or Ca 24 Al 28 O 66.
  • Examples of the isomorphous compound include, but are not limited to, the following compounds (1) to (5).
  • a compound in which some or all of Ca atoms are substituted with Sr is strontium aluminate Sr 12 Al 14 O 33 , and calcium strontium aluminum is used as a mixed crystal in which the mixing ratio of Ca and Sr is arbitrarily changed.
  • Nate Ca 12-x Sr X Al 14 O 33 (x is an integer of 1 to 11; in the case of an average value, it is a number greater than 0 and less than 12) (2)
  • Si Si, Ge, Ga, In, and B.
  • Ca 12 Al 10 Si 4 O 35 like Ca 12 Al 10 Si 4 O 35 .
  • a part of metal atoms and / or nonmetal atoms (excluding oxygen atoms) in the 12CaO.7Al 2 O 3 crystal is Ti, One or more atoms selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu, one or more alkali metal atoms selected from the group consisting of Li, Na, and K, or Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. The same type compound substituted with one or more rare earth atoms selected from the group consisting of Yb. (4) A compound in which some or all of the free oxygen ions included in the cage are replaced with other anions.
  • anions include, for example, one or more selected from the group consisting of H ⁇ , H 2 ⁇ , H 2 ⁇ , O ⁇ , O 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , and S 2 ⁇ .
  • anions and nitrogen (N) anions There are anions and nitrogen (N) anions.
  • N nitrogen
  • the “crystalline C12A7 electride” means that in the above-mentioned “crystalline C12A7”, free oxygen ions included in the cage (in the case of having other anions included in the cage, the anions) ) Means a compound in which part or all of them are substituted with electrons.
  • crystalline C12A7 electride shows electroconductivity.
  • crystalline C12A7 in which all free oxygen ions are replaced with electrons may be expressed as [Ca 24 Al 28 O 64 ] 4+ (4e ⁇ ).
  • the crystalline C12A7 electride includes Ca atoms, Al atoms, and O atoms, and the molar ratio of Ca: Al is in the range of 13:13 to 11:15, and the molar ratio of Ca: Al is 12.5: The range is preferably from 13.5 to 11.5: 14.5, and more preferably from 12.2: 13.8 to 11.8: 14.2.
  • the manufacturing method of the target made of crystalline C12A7 electride is not particularly limited.
  • the target may be manufactured using, for example, a conventional method for manufacturing a bulk crystalline C12A7 electride. For example, by heating the sintered body of crystalline C12A7 to about 1150 ° C. to 1460 ° C., preferably about 1200 ° C. to 1400 ° C. in the presence of a reducing agent such as Ti, Al, Ca or C, A target made of crystalline C12A7 electride may be manufactured. A green compact formed by compressing a crystalline C12A7 electride powder may be used as a target. By heating the sintered body of crystalline C12A7 at 1230 ° C. to 1415 ° C. in the presence of carbon and metal aluminum while keeping the sintered body and metal aluminum not in contact with each other, a large area can be efficiently obtained. A target made of crystalline C12A7 electride can be produced.
  • the electron density of the target that is, crystalline C12A7 electride is in the range of 2.0 ⁇ 10 17 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the electron density of the crystalline C12A7 electride is preferably 1 ⁇ 10 18 cm ⁇ 3 or more, more preferably 1 ⁇ 10 19 cm ⁇ 3 or more, and more preferably 1 ⁇ 10 20 cm ⁇ 3 or more. It is more preferably 5 ⁇ 10 20 cm ⁇ 3 or more, and particularly preferably 1 ⁇ 10 21 cm ⁇ 3 or more.
  • the higher the electron density of the crystalline C12A7 electride constituting the target the easier it is to obtain an electride thin film having a lower work function.
  • the electron density of crystalline C12A7 electride is more preferably 1.4 ⁇ 10 21 cm ⁇ 3 or more, and 1.7 ⁇ 10 21 cm ⁇ 3 or more is more preferable, and 2 ⁇ 10 21 cm ⁇ 3 or more is particularly preferable.
  • the electron density of the crystalline C12A7 electride is 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the electron density of the crystalline C12A7 electride is less than 2.0 ⁇ 10 17 cm ⁇ 3 , the electron density of the electride thin film obtained by film formation becomes small.
  • the electron density of the crystalline C12A7 electride can be measured by a light absorption measurement method. Since the crystalline C12A7 electride has a specific light absorption around 2.8 eV, the electron density can be determined by measuring the absorption coefficient. In particular, when the sample is a sintered body, it is convenient to use the diffuse reflection method after pulverizing the sintered body into a powder.
  • the obtained target is used as a raw material source when an amorphous oxide electride thin film is formed in the next step.
  • the surface of the target may be polished by mechanical means before use.
  • a bulk body of crystalline C12A7 electride obtained by a conventional method may have a very thin film (foreign material) on the surface.
  • the composition of the obtained thin film may deviate from a desired composition ratio.
  • such a problem can be significantly suppressed by carrying out the polishing treatment of the target surface.
  • Step S122 film formation is performed on the semiconductor layer by a vapor deposition method using the target manufactured in the above-described step S121.
  • vapor deposition refers to vapor deposition of a target material including a physical vapor deposition (PVD) method, a PLD method, a sputtering method, and a vacuum deposition method, and then depositing this material on a substrate.
  • PVD physical vapor deposition
  • PLD physical vapor deposition
  • sputtering method a sputtering method
  • vacuum deposition method a vacuum deposition method
  • the sputtering method is particularly preferable.
  • a thin film can be formed relatively uniformly in a large area.
  • the sputtering method includes a DC (direct current) sputtering method, a high frequency sputtering method, a helicon wave sputtering method, an ion beam sputtering method, a magnetron sputtering method, and the like.
  • step S122 will be described by taking as an example the case where film formation is performed by sputtering.
  • the temperature of the substrate on which the thin film of electride is formed is not particularly limited, and any temperature in the range from room temperature to, for example, 700 ° C. may be adopted. It should be noted that the substrate need not necessarily be “positively” heated when depositing the electride thin film. However, there may be a case where the temperature of the deposition target substrate rises “incidentally” due to the radiant heat of the vapor deposition source. For example, the temperature of the deposition target substrate may be 500 ° C. or lower, or 200 ° C. or lower.
  • the film formation substrate is not “positively” heated, it is possible to use, as the substrate material, a material whose heat resistance is reduced on the high temperature side exceeding 700 ° C., such as glass or plastic.
  • the oxygen partial pressure during film formation is preferably less than 0.1 Pa.
  • the oxygen partial pressure is preferably 0.01 Pa or less, more preferably 1 ⁇ 10 ⁇ 3 Pa or less, further preferably 1 ⁇ 10 ⁇ 4 Pa or less, and 1 ⁇ 10 ⁇ 5 Pa or less. It is particularly preferred that When the oxygen partial pressure is 0.1 Pa or more, oxygen is taken into the deposited thin film, which may reduce the electron density.
  • the hydrogen partial pressure during film formation is preferably less than 0.004 Pa.
  • the pressure is 0.004 Pa or more, hydrogen or OH component is taken into the formed thin film, which may reduce the electron density of the amorphous oxide electride thin film.
  • the sputtering gas used is not particularly limited.
  • the sputtering gas may be an inert gas or a rare gas.
  • the inert gas eg, N 2 gas.
  • examples of the rare gas include He (helium), Ne (neon), Ar (argon), Kr (krypton), and Xe (xenon). These may be used alone or in combination with other gases.
  • the sputtering gas may be a reducing gas such as NO (nitrogen monoxide).
  • the pressure of the sputtering gas is not particularly limited, and can be freely selected so that a desired thin film can be obtained.
  • the pressure P (Pa) of the sputtering gas (pressure in the chamber) is such that when the distance between the substrate and the target is t (m) and the diameter of the gas molecule is d (m), 8.9 ⁇ 10 ⁇ 22 / (td 2 ) ⁇ P ⁇ 4.5 ⁇ 10 ⁇ 20 / (td 2 ) (3) Formula It may be selected to satisfy.
  • the mean free path of the sputtered particles becomes substantially equal to the distance between the target and the deposition target substrate, and the sputtered particles are prevented from reacting with the remaining oxygen.
  • a sputtering method apparatus it is possible to use an inexpensive and simple vacuum apparatus having a relatively high back pressure.
  • the method of forming an amorphous oxide electride thin film has been briefly described by taking the sputtering method as an example.
  • the method of forming the amorphous oxide electride thin film is not limited to this, and the above-described two steps (steps S121 and S122) may be appropriately changed or various steps may be added. It is clear that it is also good.
  • a pre-sputtering process (a dry etching process of the target) may be performed on the target before starting the formation of the amorphous oxide electride by the sputtering method. .
  • the surface of the target is cleaned, and it becomes easy to form a thin film having a desired composition in the subsequent film formation process (main film formation).
  • the target when the target is used for a long time, oxygen is taken into the surface of the target, and the electron density of the crystalline C12A7 electride constituting the target may decrease.
  • the composition of the target when the target is used for a long time, the composition of the target may deviate from the initial composition due to the difference in sputtering rate of each component constituting the target (ie, crystalline C12A7 electride).
  • the composition may deviate from a desired value even in the formed thin film.
  • such a problem is suppressed by performing the pre-sputtering process.
  • the gas used in the pre-sputtering process may be the same as or different from the sputtering gas used in the main film formation.
  • the gas used for the pre-sputtering process is preferably He (helium), Ne (neon), N 2 (nitrogen), Ar (argon), and / or NO (nitrogen monoxide).
  • an electride thin film is formed on the patterned semiconductor layer 105.
  • the first and / or second electride thin films 150a and 150b can be formed by patterning the electride thin film into a desired pattern by a photolithography process or the like.
  • the semiconductor layer 105 is an oxide semiconductor
  • the semiconductor layer 105 and the thin film of the electride can be continuously formed by a sputtering method without exposing the deposition target substrate to the atmosphere.
  • the semiconductor layer 105 and the electride thin film are preferably formed in succession.
  • the electride thin film is preferably heat-treated after patterning.
  • the heat treatment temperature is preferably 300 ° C. or higher, more preferably 500 ° C. or higher.
  • the temperature is lower than the temperature at which the coating film and the deposition target substrate can withstand, and is preferably 700 ° C. or lower.
  • the holding time at a predetermined temperature may be 1 minute to 2 hours, or 10 minutes to 1 hour.
  • the timing of the heat treatment may be after patterning the electride thin film, after forming the source electrode and the drain electrode on the electride thin film (for example, the example of FIG. 3), or the electride thin film. It may be after the semiconductor layer is formed thereon (for example, the example of FIG. 4). By heat treatment, recovery can be achieved when the thin film of electride is damaged during patterning.
  • Step S130 Next, the source electrode 120 and the drain electrode 122 are formed on the first and / or second electride thin films 150a and 150b.
  • the source electrode 120 and the drain electrode 122 various conventional methods can be used.
  • the source electrode 120 and the drain electrode 122 can be formed by performing a photolithography process or the like on the film after forming the conductive layer for forming the source electrode 120 and the drain electrode 122.
  • the source electrode 120 is disposed on the first electride thin film 150a, and / or the drain electrode 122 is disposed on the second electride thin film 150b.
  • the contact resistance at the interface between the source electrode 120 and the semiconductor layer 105 and / or the interface between the drain electrode 122 and the semiconductor layer 105 is reduced.
  • the semiconductor layer may have a portion in direct contact with the source electrode and / or the drain electrode.
  • a thin film of a semiconductor layer and an electride is continuously formed and patterned in a lump by a photolithography process. The side surface of the pattern of the semiconductor layer is likely not to be covered with the electride thin film.
  • a source electrode and a drain electrode are formed on the electride thin film. At this time, the side surface of the pattern of the semiconductor layer may be in contact with the source electrode and the drain electrode.
  • Step S140 Next, a gate insulating film 130 is formed so as to cover the source electrode 120 and the drain electrode 122.
  • the gate insulating film 130 may be formed by a coating method such as a dipping method, a spin coating method, a droplet discharge method, a casting method, a spinner method, or a printing method, or a CVD method or a sputtering method.
  • a coating method such as a dipping method, a spin coating method, a droplet discharge method, a casting method, a spinner method, or a printing method, or a CVD method or a sputtering method.
  • a gate electrode 124 is formed on the gate insulating film 130.
  • Various methods conventionally used can be used to form the gate electrode 124.
  • the gate electrode 124 may be formed by a sputtering method, an evaporation method, or the like.
  • the gate electrode 124 can be formed by performing a photolithography process or the like on the film after forming the conductive layer for forming the gate electrode 124.
  • the first semiconductor device 100 can be manufactured.
  • the semiconductor device 400, the semiconductor device 500, and further the semiconductor device 600 can be manufactured by the same method. That is, by changing the order of the steps shown in FIG. 7, the semiconductor device having each configuration can be manufactured.
  • a transparent semiconductor device can be manufactured by using all the substrates, electrodes, and semiconductor layers used in the semiconductor device of the present invention as transparent materials.
  • the semiconductor device of the present invention can be used for a light emitting display device.
  • the organic electroluminescence element included in the light emitting display device may have any of the following configurations. (1) A substrate, an anode, and a cathode are provided in this order, and the substrate side is a light extraction surface. An electride thin film exists between the anode and the cathode, or constitutes a cathode. (2) A substrate, an anode, and a cathode are provided in this order, and the cathode side is a light extraction surface, and a thin film of electride exists between the anode and the cathode, or constitutes the cathode.
  • a substrate, a cathode, and an anode are provided in this order, and the substrate side is a light extraction surface, and an electride thin film exists between the anode and the cathode or constitutes the cathode.
  • a substrate, a cathode, and an anode are provided in this order, and the anode side is a light extraction surface, and an electride thin film exists between the anode and the cathode or constitutes the cathode.
  • the “electride thin film” included in the organic electroluminescence element may be “an amorphous oxide electride thin film including calcium atoms and aluminum atoms” included in the semiconductor device of the present invention.
  • the organic electroluminescence element may have a configuration in which a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially provided between the anode and the cathode.
  • the hole injection layer, the hole transport layer, the electron transport layer, and / or the electron injection layer may be omitted.
  • the thin film of electride can constitute, for example, an electron injection layer.
  • an electron transport layer made of a metal oxide may be disposed between the light emitting layer and the electron injection layer (electride thin film).
  • the electron transport layer may be in the form of amorphous, crystalline, or a mixed phase of amorphous and crystalline.
  • the electron transport layer may be composed of ZnO—SiO 2 , In 2 O 3 —SiO 2 , SnO 2 —SiO 2 , ZnO, In—Ga—Zn—O, In—Zn—O, or SnO 2. good.
  • the present invention can be applied to, for example, a semiconductor device used for various electronic devices such as an electro-optical device.
  • a semiconductor device used for various electronic devices such as an electro-optical device.
  • it can be used for electronic devices such as displays such as televisions, electrical appliances such as washing machines and refrigerators, and information processing devices such as mobile phones and computers.
  • the semiconductor device of the present invention can also be used for electronic devices included in automobiles and various industrial equipment.

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Abstract

L'objet de la présente invention est de réduire la résistance de contact entre une électrode source et une couche semi-conductrice, et la résistance de contact entre une électrode drain et la couche semi-conductrice. La présente invention concerne un dispositif à semi-conducteur (100) présentant une électrode source (120), une électrode drain (122), une électrode grille (124) et une couche semi-conductrice (105). Le dispositif à semi-conducteur (100) est caractérisé en ce qu'il présente de minces couches d'électrode (150a, 150b) d'un oxyde amorphe entre la couche semi-conductrice (105) et l'électrode source (120) et/ou l'électrode drain (122), ledit oxyde amorphe contenant des atomes de calcium et des atomes d'aluminium.
PCT/JP2014/063873 2013-05-28 2014-05-26 Dispositif à semi-conducteur et procédé de fabrication d'un dispositif à semi-conducteur WO2014192701A1 (fr)

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US20200044041A1 (en) * 2018-08-06 2020-02-06 Samsung Electronics Co., Ltd. Transistor including electride electrode
WO2023079877A1 (fr) * 2021-11-08 2023-05-11 Ａｇｃ株式会社 Électrolyte solide conducteur d'ions oxydes

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