WO2016006297A1

WO2016006297A1 - Electronic device, manufacturing method therefor, solid-state imaging device, and insulating material

Info

Publication number: WO2016006297A1
Application number: PCT/JP2015/061809
Authority: WO
Inventors: 俊貴森脇
Original assignee: ソニー株式会社
Priority date: 2014-07-07
Filing date: 2015-04-17
Publication date: 2016-01-14

Abstract

An electronic device which is equipped with: a light-emitting/light-receiving layer (20); a first electrode (31) which is electrically connected to the light-emitting/light-receiving layer; and a second electrode (32) which is formed on the light-emitting/light-receiving layer (30). The second electrode (32) comprises at least a quaternary compound of: indium; gallium and/or aluminium; zinc; and oxygen. The light emitting/light-receiving layer (20) is coated by an insulating layer (40) that comprises at least a quaternary compound of: indium; gallium and/or aluminium; zinc; and oxygen. The composition ratio of oxygen in the insulating layer (40) is higher than the composition ratio of oxygen in the second electrode (32).

Description

Electronic device and method for manufacturing the same, solid-state imaging device, and insulating material

The present disclosure relates to an electronic device and a manufacturing method thereof, a solid-state imaging apparatus incorporating the electronic device, and an insulating material.

For example, an electronic device including a photoelectric conversion element such as an image sensor is configured, for example, by sequentially stacking a first electrode, a light emitting / receiving layer constituting a photoelectric conversion site, and a second electrode. The second electrode is a transparent electrode, which collects electrons with one electrode and collects holes with the other electrode to read out photocurrent. When the light emitting / receiving layer is made of, for example, an organic material, it is known that the light emitting / receiving layer is deteriorated by moisture or oxygen. Therefore, for example, the deterioration of the light emitting / receiving layer is suppressed by covering the second electrode with an insulating layer functioning as a protective layer (see, for example, JP-A-2013-118363).

JP2013-118363A

By the way, in the technique disclosed in the above patent publication, the insulating layer is composed of a single layer of a silicon oxynitride layer, or alternatively, a two-layer structure of a silicon oxynitride layer (upper layer) / aluminum oxide layer or the like (lower layer). The film is formed based on the vapor phase growth method. The second electrode (counter electrode) is composed of a metal, a metal oxide, a metal nitride, a metal boride, an organic conductive compound, a mixture thereof, or the like. That is, the second electrode and the insulating layer are made of completely different materials. Therefore, it is necessary to form the second electrode and the insulating layer based on different processes. That is, there is a problem that the formation of the second electrode and the formation of the insulating layer cannot be performed based on a series of processes, and the electronic device cannot be manufactured by a more rational method. The insulating layer is formed based on, for example, an atomic layer volume method such as a plasma CVD method or an ALCVD method. The film formation temperature at this time is 150 ° C. to 250 ° C. or 100 ° C. to 200 ° C. is there.

Accordingly, it is an object of the present disclosure to provide an electronic device manufacturing method capable of being manufactured in a more rational method or in a lower temperature process, an electronic device obtainable by such a method, and such an electronic device It is an object of the present invention to provide a solid-state imaging device incorporating an insulating material and an insulating material.

In order to achieve the above object, an electronic device of the present disclosure is provided.
A light emitting / receiving layer, a first electrode electrically connected to the light emitting / receiving layer, and a second electrode formed on the light emitting / receiving layer,
The second electrode is composed of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O).
The light emitting / receiving layer is covered with an insulating layer composed of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O). Has been
The composition ratio of oxygen (O) in the insulating layer is higher than the composition ratio of oxygen (O) in the second electrode.

The solid-state imaging device of the present disclosure for achieving the above object includes the electronic device of the present disclosure.

In order to achieve the above object, a method of manufacturing an electronic device according to the present disclosure includes:
A second electrode composed of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O) on the light emitting / receiving layer. Is formed based on the sputtering method, and then
The light emitting / receiving layer is composed of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O) based on a sputtering method. Covered with an insulating layer,
Including at least a step,
By controlling the oxygen gas partial pressure (oxygen gas introduction amount) when forming the second electrode and the insulating layer based on the sputtering method, the composition ratio of oxygen (O) in the insulating layer is changed to oxygen (O) in the second electrode. Higher than the composition ratio.

In order to achieve the above object, an insulating material of the present disclosure includes at least a quaternary system of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O). It is composed of compounds.

In the present disclosure, the composition of the second electrode and the insulating layer and the composition ratio of oxygen are defined, and the second electrode and the insulating layer can be formed of the same kind of material. In addition, it becomes possible to manufacture an electronic device by a process at a lower temperature, and even though the second electrode and the insulating layer are made of the same material, they impart conductivity and insulating properties to each. can do. Note that the effects described in the present specification are merely examples and are not limited, and may have additional effects.

1A and 1B are schematic partial cross-sectional views of the electronic device of the first embodiment and its modification, and FIG. 1C is a schematic partial cross-sectional view of the electronic device of the third embodiment. FIG. 2 is a graph showing the results of examining the relationship between the oxygen gas partial pressure during film formation and the internal stress of the obtained IGZO film in Example 1. FIG. 3A shows an example of a result obtained by obtaining a relationship between an oxygen gas introduction amount (oxygen gas partial pressure) and a work function value of the first electrode when forming the first electrode based on the sputtering method in Example 2. FIG. 3B is a graph of IV curves obtained in the electronic devices of Example 2, Example 3, and Comparative Example 2. 4A and 4B are conceptual diagrams of energy diagrams in the electronic devices of Example 2 and Comparative Example 2, respectively. FIGS. 4C and 4D are work functions in the electronic devices of Example 2 and Comparative Example 2, respectively. It is a conceptual diagram which shows the correlation with the difference of the value of and an energy diagram. FIG. 5A and FIG. 5B are graphs showing the correlation between the internal quantum efficiency and the difference between the work function values and the correlation between the dark current and the difference between the work function values in the electronic device of Example 2, respectively. 6A and 6B are graphs showing the correlation between the internal quantum efficiency and the difference between the work function values in the electronic device of Example 3, and the correlation between the dark current and the difference between the work function values, respectively. 7A and 7B are schematic partial cross-sectional views of the electronic device of Example 4. FIG. FIG. 8 is a schematic partial cross-sectional view of a modification of the electronic device of the fourth embodiment. FIG. 9 is a scanning transmission electron microscope image of the electronic device of Example 4. FIG. 10 is a diagram showing the relationship between the series resistance value of the electronic device and the value of the work function of the material constituting the p-side electrode. FIG. 11A and FIG. 11B are schematic partial cross-sectional views of the electronic device of Example 6 and its modification. FIG. 12 is a conceptual diagram of the solid-state imaging device according to the seventh embodiment. FIG. 13 is a diagram showing the relationship between the second electrode formed on the second compound semiconductor layer made of p-type GaN and the resistance value.

Hereinafter, although this indication is explained based on an example with reference to drawings, this indication is not limited to an example and various numerical values and materials in an example are illustrations. The description will be given in the following order.
1. 1. Description of electronic device and manufacturing method thereof, solid-state imaging device, and insulating material of the present disclosure Example 1 (Electronic Device of the Present Disclosure and Method for Producing the Same, Electronic Device of Configuration 1-C, and Insulating Material of the Present Disclosure)
3. Example 2 (Modification of Example 1, Electronic Device with Configuration 1-A, Electronic Device with Configuration 1-C)
4). Example 3 (another modification of Example 1, an electronic device having a first-B configuration, and an electronic device having a first-C configuration)
5. Example 4 (another modification of Example 1, electronic device having configuration 2-A)
6). Example 5 (Modification of Example 4)
7). Example 6 (another modification of Example 1, electronic device having the configuration 2-B)
8). Example 7 (Solid-state imaging device of the present disclosure)
9. Other

<Description of Electronic Device of the Present Disclosure and Method for Manufacturing the Same, Solid-State Imaging Device, and Insulating Material>
In the method of manufacturing an electronic device according to the present disclosure, the oxygen gas partial pressure when forming the insulating layer based on the sputtering method is not limited, but is preferably 0.04 Pa to 0.15 Pa. And in the manufacturing method of the electronic device of this indication containing such a preferable form, the temperature at the time of forming an insulating layer based on sputtering method shall be room temperature or 22 to 28 degreeC. It is preferable. Furthermore, in the manufacturing method of the electronic device of the present disclosure including these preferable modes, the electronic device can be configured to constitute a photoelectric conversion element.

The electronic device of the present disclosure and the electronic device obtained by the manufacturing method of the electronic device of the present disclosure including the various preferred embodiments described above (hereinafter, these are collectively referred to as “electronic device etc. of the present disclosure”). In some cases)
The second electrode is made of In _a (Ga, Al) _b Zn _c O _d ,
The insulating layer may be made of In _a (Ga, Al) _b Zn _c O _e (where d <e). Note that the second electrode and the insulating layer are preferably in an amorphous state.

In the electronic device or the like of the present disclosure including the various preferable embodiments described above, the insulating layer and the second electrode are indium-gallium oxide (IGO), indium-doped gallium-zinc oxide (IGZO, In-GaZnO). ₄ ) may be made of a transparent conductive material such as aluminum oxide-doped zinc oxide (AZO), indium-zinc oxide (IZO), or gallium-doped zinc oxide (GZO). it can.

Furthermore, in the electronic device and the like of the present disclosure including the various preferable forms described above, the internal stress of the insulating layer can be a form having a compressive stress of 10 MPa to 90 MPa.

Furthermore, in the electronic device of the present disclosure including the various preferable forms described above, the light transmittance of the insulating layer with respect to light having a wavelength of 400 nm to 660 nm can be 80% or more.

Furthermore, in the electronic device of the present disclosure including the various preferable forms described above, the light transmittance of the second electrode with respect to light having a wavelength of 400 nm to 660 nm may be 75% or more.

Furthermore, in the electronic device of the present disclosure including the various preferable forms described above, the sheet resistance value of the second electrode may be 3 × 10 Ω / □ to 1 × 10 ³ Ω / □. .

Furthermore, in the electronic device of the present disclosure including the various preferable embodiments described above, the oxygen gas partial pressure (oxygen gas introduction amount) when the second electrode and the insulating layer are formed based on the sputtering method is controlled. Thus, the composition ratio of oxygen (O) in the second electrode and the insulating layer can be controlled.

Furthermore, in the electronic device of the present disclosure including the various preferred embodiments described above,
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The difference between the work function value of the second electrode and the work function value of the first electrode may be 0.4 eV or more. Note that the electronic device of the present disclosure having such a configuration is referred to as an “electronic device having the first-A configuration” for convenience.

Alternatively, in the electronic device and the like of the present disclosure including the various preferable modes described above,
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The second electrode has a laminated structure of the second B layer and the second A layer from the light emitting / receiving layer side,
The work function value of the second A layer of the second electrode may be lower than the work function value of the second B layer of the second electrode. Note that the electronic device of the present disclosure having such a configuration is referred to as an “electronic device having the configuration of 1-B” for convenience.

In the electronic device having the configuration 1-A, since the difference between the work function value of the second electrode and the work function value of the first electrode is defined, the difference between the first electrode and the second electrode is determined. When a bias voltage is applied between them, the internal quantum efficiency can be improved and the generation of dark current can be suppressed. In the electronic device having the configuration 1-B, the second electrode has a two-layer structure of the second A layer and the second B layer, and the work function difference between the second B layer and the second A layer is small. Since it is defined, the work function in the second electrode can be optimized, and the transfer (transfer) of the carrier becomes easier. In the manufacture of the electronic device having the configuration 1-A, the work function value of the second electrode is set by controlling the oxygen gas partial pressure (oxygen gas introduction amount) when forming based on the sputtering method. As a result of control, it is possible to generate a large internal electric field in the light emitting / receiving layer based on the difference in the work function value, improve internal quantum efficiency, and suppress the generation of dark current The electronic device that can be manufactured can be manufactured by a simple manufacturing process. In the manufacture of the electronic device having the configuration 1-B, the second A layer and the second B layer of the second electrode are controlled by controlling the oxygen gas partial pressure (oxygen gas introduction amount) when forming based on the sputtering method. As a result, the work function of the second electrode can be optimized.

In the electronic device having the configuration 1-A, the difference between the work function value of the second electrode and the work function value of the first electrode is 0.4 eV or more. Based on this difference, an internal electric field can be generated in the light emitting / receiving layer to improve the internal quantum efficiency. In the electronic device having the configuration 1-A, the thickness of the second electrode is preferably 1 × 10 ⁻⁸ m to 1 × 10 ⁻⁷ m.

In the electronic device having the configuration 1-B, the difference between the work function value of the second electrode 2A layer and the work function value of the second electrode layer 2B is 0.1 eV to 0.2 eV. It can be set as the structure which is. Furthermore, in these configurations, the difference between the work function value of the first electrode and the work function value of the second A layer of the second electrode is preferably 0.4 eV or more. Further, in the electronic device having the first-B configuration including the preferable configuration described above, the thickness of the second electrode is 1 × 10 ⁻⁸ m to 1 × 10 ⁻⁷ m, and the second electrode The ratio of the thickness of the 2A layer and the thickness of the second B layer of the second electrode may be 9/1 to 1/9. In order to reduce the influence of oxygen atoms and oxygen molecules on the light emitting / receiving layer, it is more preferable that the thickness of the second B layer is smaller than the thickness of the second A layer of the second electrode. Further, in the electronic device having the first-B configuration including the preferable configuration described above, the difference between the work function value of the first electrode and the work function value of the second A layer of the second electrode is set to 0.4 eV. With the above, it is preferable to improve the internal quantum efficiency by generating an internal electric field in the light emitting / receiving layer based on the difference in the work function values.

Furthermore, in the electronic device having the first-A configuration or the electronic device having the first-B configuration including the preferred configuration described above, the value of the work function of the second electrode is not limited, The configuration may be 4.1 eV to 4.5 eV.

Furthermore, in the electronic device having the first-A configuration including the preferred configuration described above or the electronic device having the first-B configuration, as described above, the second electrode includes indium-gallium oxide (IGO), Indium-doped gallium-zinc oxide (IGZO, In-GaZnO ₄ ), aluminum oxide-doped zinc oxide (AZO), indium-zinc oxide (IZO), or gallium-doped zinc oxide (GZO) The work function value of the second electrode made of these transparent conductive materials can be 4.1 eV to 4.5 eV, for example. Further, in the electronic device having the 1-A configuration or the 1-B configuration including these preferable configurations, the first electrode is composed of indium-tin oxide (ITO), indium-zinc oxide (IZO). Or a transparent conductive material such as tin oxide (SnO ₂ ). In addition, the value of the work function of the 1st electrode comprised from these transparent conductive materials is 4.8 eV thru | or 5.0 eV, for example.

Further, in the electronic device having the first-A configuration or the first-B configuration including the preferred configuration described above, the oxygen gas partial pressure (oxygen gas) when the second electrode is formed by sputtering is used. By controlling the gas introduction amount), the work function value of the second electrode can be controlled. Further, the work function values of the second A layer and the second B layer of the second electrode are controlled by controlling the oxygen gas partial pressure (oxygen gas introduction amount) when forming the second electrode based on the sputtering method. It can be configured. In the second electrode, the oxygen content may be lower than the oxygen content of the stoichiometric composition. Alternatively, the oxygen content of the second A layer of the second electrode can be lower than the oxygen content of the second B layer of the second electrode. Then, the work function value of the second electrode can be controlled based on the oxygen content, and the oxygen content becomes smaller than the oxygen content of the stoichiometric composition, that is, oxygen deficiency increases. As the value of the work function decreases.

In the electronic device having the first-A configuration or the first-B configuration including the preferred configuration described above, specifically, for example, the first electrode is formed on the substrate, and The light receiving layer may be formed on the first electrode, and the second electrode may be formed on the light emitting / light receiving layer. That is, the electronic device or the like of the present disclosure has a two-terminal electronic device structure including the first electrode and the second electrode. However, the present invention is not limited to this, and a three-terminal electronic device structure provided with a control electrode may be used, and the current flowing can be modulated by applying a voltage to the control electrode. Specifically, as a three-terminal electronic device structure, a so-called bottom gate / bottom contact type, bottom gate / top contact type, top gate / bottom contact type, top gate / top contact type field effect transistor (FET) and The same structure and structure can be mentioned. The second electrode can function as a cathode electrode (cathode) (that is, function as an electrode that extracts electrons), while the first electrode can function as an anode electrode (anode) (that is, an electrode that extracts holes). Function as). It is also possible to adopt a structure in which a plurality of electronic devices or the like having different light absorption spectra in the light emitting / receiving layers are stacked. In addition, for example, a structure in which a substrate is formed of a silicon semiconductor substrate, a drive circuit such as an electronic device or a light emitting / receiving layer is provided on the silicon semiconductor substrate, and the electronic device is stacked on the silicon semiconductor substrate is employed. You can also

In the electronic device having the first-A configuration including the preferred configuration described above or the electronic device of the present disclosure including the first-B configuration, the light emitting / receiving layer may be in an amorphous state or a crystal It may be in a state. Examples of the organic material (organic photoelectric conversion material) constituting the light emitting / receiving layer include organic semiconductor materials, organometallic compounds, and organic semiconductor fine particles, or metal oxide as the material constituting the light emitting / receiving layer. Examples thereof include a physical semiconductor, inorganic semiconductor fine particles, a material in which a core member is covered with a shell member, and an organic-inorganic hybrid compound. For the sake of convenience, the electronic device or the like of the present disclosure having such a configuration (including the electronic device having the first-A configuration and the electronic device having the first-B configuration) is referred to as “the electronic device having the first-C configuration”. Call it.

Here, as an organic semiconductor material, specifically, an organic dye represented by quinacridone and its derivatives, a previous period represented by Alq3 [tris (8-quinolinolato) aluminum (III)] (metal on the left side of the periodic table) Dyes obtained by chelating ions with an organic material, organometallic dyes complexed with a transition metal ion typified by zinc phthalocyanine (II), and dinaphthothienothiophene (DNTT). .

Specific examples of the organometallic compound include a dye obtained by chelating the above-described periodic ions with an organic material, and an organometallic dye complexed with a transition metal ion and an organic material. As organic semiconductor fine particles, specifically, organic dye aggregates represented by the above-mentioned quinacridone and derivatives thereof, dye aggregates obtained by chelating the precursor ions with organic materials, and complex formation with transition metal ions and organic materials And an organic metal dye aggregate, or Prussian blue obtained by crosslinking a metal ion with a cyano group and derivatives thereof, or a complex aggregate thereof.

As the metal oxide semiconductor or inorganic semiconductor fine particles, specifically, ITO, IGZO, ZnO, IZO, IrO ₂ , TiO ₂ , SnO ₂ , SiO _x , karogen [for example, sulfur (S), selenium (Se), tellurium (Te)] can be given as metal karogen semiconductors (specifically, CdS, CdSe, ZnS, CdSe / CdS, CdSe / ZnS, PbSe), ZnO, CdTe, GaAs, and Si.

As a combination of a material in which a core member is covered with a shell member, that is, a combination of (core member, shell member), specifically, an organic material such as (polystyrene, polyaniline), a metal material that is difficult to ionize, or a metal that is easily ionized Metal material). Specific examples of organic-inorganic hybrid compounds include Prussian blue in which metal ions are cross-linked with cyano groups and derivatives thereof. In addition, compounds in which metal ions are infinitely cross-linked with bipyridines, oxalic acid, rubeanic acid Coordination polymer (Coordination Polymer), which is a generic name of cross-linked metal ions with polyvalent ionic acids represented by

In the electronic device having the 1st-C structure, various chemical methods including a coating method, a physical vapor deposition method (PVD method), and a MOCVD method are used as a method for forming a light emitting / receiving layer depending on a material to be used. A vapor phase growth method (CVD method) can be mentioned. Here, as a coating method, specifically, spin coating method; dipping method; casting method; various printing methods such as screen printing method, inkjet printing method, offset printing method, gravure printing method; stamp method; spray method; air doctor Coater method, blade coater method, rod coater method, knife coater method, squeeze coater method, reverse roll coater method, transfer roll coater method, gravure coater method, kiss coater method, cast coater method, spray coater method, slit orifice coater method, calendar Various coating methods such as a coater method can be exemplified. In the coating method, examples of the solvent include nonpolar or low polarity organic solvents such as toluene, chloroform, hexane, and ethanol. Further, as the PVD method, various vacuum deposition methods such as an electron beam heating method, a resistance heating method, and a flash deposition method; a plasma deposition method; a bipolar sputtering method, a direct current sputtering method, a direct current magnetron sputtering method, a high frequency sputtering method, a magnetron sputtering method, Various sputtering methods such as ion beam sputtering and bias sputtering; DC (direct current) method, RF method, multi-cathode method, activation reaction method, field deposition method, high-frequency ion plating method, reactive ion plating method, etc. Examples of various ion plating methods can be given.

Further, in the electronic device having the first-C configuration, the thickness of the light emitting / receiving layer is not limited. For example, the thickness may be 1 × 10 ⁻¹⁰ m to 5 × 10 ⁻⁷ m. .

Furthermore, in the electronic device having the 1-C configuration, as a substrate, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyethersulfone (PES), polyimide, Organic polymers such as polycarbonate (PC), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN) (polymer materials such as flexible plastic films, plastic sheets and plastic substrates made of polymer materials) Can be included). By using a substrate made of such a flexible polymer material, for example, an electronic device can be incorporated or integrated into an electronic device having a curved surface. Alternatively, as a substrate, various glass substrates, various glass substrates with an insulating film formed on the surface, quartz substrates, quartz substrates with an insulating film formed on the surface, silicon semiconductor substrates, silicon with an insulating film formed on the surface Examples include semiconductor substrates, metal substrates made of various alloys such as stainless steel, and various metals. As the insulating film, a silicon oxide-based material (for example, SiO _x or spin-on glass (SOG)); silicon nitride (SiN _Y ); silicon oxynitride (SiON); aluminum oxide (Al ₂ O ₃ ); metal oxide or Mention may be made of metal salts. In addition, a conductive substrate (a substrate made of a metal such as gold or aluminum or a substrate made of highly oriented graphite) having these insulating films formed on the surface can also be used. The surface of the substrate is desirably smooth, but may have a roughness that does not adversely affect the characteristics of the light emitting / receiving layer. A silanol derivative is formed on the surface of the substrate by a silane coupling method, a thin film made of a thiol derivative, a carboxylic acid derivative, a phosphoric acid derivative, or the like is formed by a SAM method, or an insulating metal salt or metal is formed by a CVD method. You may improve the adhesiveness between a 1st electrode or a 2nd electrode, and a board | substrate by forming the thin film which consists of a complex.

Furthermore, in the electronic device and the like of the present disclosure including the various preferable modes and configurations described above, the light emitting / receiving layer can be configured of an organic photoelectric conversion material.

Furthermore, in the electronic device and the like of the present disclosure including the various preferable forms and configurations described above, the electronic device can be configured by a photoelectric conversion element.

In the electronic device of the present disclosure including the various preferable modes and configurations described above, light emission / light reception in the light emission / light reception layer (generally electromagnetic waves, including visible light, ultraviolet rays, and infrared rays) is second. It may be performed via the electrode or may be performed via the first electrode. In the latter case, it is necessary to use a substrate that is transparent to the light emitted and received.

The electronic device of the present disclosure including the various preferable modes and configurations described above can be applied to the electronic device constituting the solid-state imaging device of the present disclosure.

A semiconductor optical device typified by a semiconductor laser element or a light emitting diode includes, for example, a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound having a second conductivity type different from the first conductivity type. It has a laminated structure (light emitting / receiving layer) made of a semiconductor layer, a second electrode is formed on the second compound semiconductor layer, and the first compound semiconductor layer is electrically connected to the first electrode. It has a structure.

FIG. 13 (Source: Ishikawa, et.al., J. Appl. Phys. 81. 1315 (1997)) shows the second electrode (p-side electrode) formed on the second compound semiconductor layer made of p-type GaN. The relationship between the metal which comprises and resistance value is shown. The black circles indicate values before annealing, and the white circles indicate values after annealing at 500 ° C. As for the second electrode for the second compound semiconductor layer made of p-type GaN, a metal having a larger work function has a lower Schottky barrier, so that good contact characteristics tend to be obtained. FIG. 13 shows that the resistance value decreases as the work function value of the metal increases. Therefore, in general, a platinum group such as Pd and Pt having a work function value distributed between 5 eV and 5.65 eV, Ni, Au, and the like are used as an ohmic electrode for the second compound semiconductor layer made of p-type GaN. It has been. However, there is a strong demand for further increasing the degree of freedom in selecting the material constituting the second electrode.

In order to cope with such a demand, in the electronic device of the present disclosure including the various preferable modes described above,
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A second electrode is formed on the second compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the second compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the second compound semiconductor layer in contact with the contact layer is along the x ₂ and z axes. When the lattice constant is z ₂ , the length along the x-axis in one unit of the crystal constituting the contact layer is x _C ′, and the length along the z-axis is z _C ′,
(Z _C '/ x _C ')> (z ₂ / x ₂ )
It can be set as the structure which satisfies these. Note that the electronic device of the present disclosure having such a configuration is referred to as an “electronic device having a configuration of 2-A” for convenience.

Alternatively, in order to cope with such a demand, in the electronic device of the present disclosure including the various preferable modes described above,
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A first electrode is formed on the first compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the first compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the first compound semiconductor layer in contact with the contact layer is along the x ₁ and z axes. When the lattice constant is z ₁ , the length along the x-axis in one unit of the crystal constituting the contact layer is x _C ″, and the length along the z-axis is z _C ″
(Z _C ″ / x _C ″)> (z ₁ / x ₁ )
It can be set as the structure which satisfies these. Note that the electronic device or the like of the present disclosure having such a configuration is referred to as an “electronic device having a second-B configuration” for convenience.

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, the lattice constant in the interface layer which is a part of the second compound semiconductor layer or the first compound semiconductor layer in contact with the contact layer; Since the length of one unit of crystal constituting the contact layer satisfies a predetermined relationship, a kind of distortion occurs in the contact layer, and as a result, not only can the drive voltage be reduced. The second electrode or the first electrode can be formed from a material having a low work function value, and the degree of freedom in selecting the material forming the second electrode or the first electrode can be improved.

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, the thickness of the contact layer is 4 atomic layers or less. If the thickness of the contact layer exceeds 4 atomic layers, crystal defects may occur in the contact layer, which may increase the contact resistance value. The contact layer may be “layered” or may be formed in an island shape (island shape) and not in a layered state.

In the electronic device having the configuration 2-A, the contact layer may be configured to be pseudo-lattice matched with the interface layer of the second compound semiconductor layer. Here, pseudo-matching means that the value of x _C ′ is equal to the value of x ₂ , and the volume of one unit of the crystal constituting the contact layer is determined from the lattice constant of the crystal constituting the contact layer. Means equal to the required volume. That is, in the electronic device having the configuration 2-A having such a configuration, when the lattice constant along the x axis of the crystal constituting the contact layer is x _C and the lattice constant along the z axis is z _C ,
x ₂ = x _C '<x _C
z _C '> z _C
It can be set as the structure which satisfies these. Although expressed as “x ₂ = x _C ′”, this expression is not only mathematically strictly equal,
0.90 ≦ x _C ′ / x ₂ ≦ 1.10
Is included.

Further, in the electronic device having the configuration 2-B, the contact layer can be configured to be pseudo-lattice matched with the interface layer of the first compound semiconductor layer. Here, pseudo-lattice matching means that the value of x _C ″ is equal to the value of x ₁ , and the volume of one unit of the crystal constituting the contact layer is determined from the lattice constant of the crystal constituting the contact layer. In other words, in the electronic device having the configuration 2-B, the lattice constant along the x-axis of the crystal forming the contact layer is expressed as x _C , along the z-axis. When the lattice constant is z _C ,
x ₁ = x _C ″ <x _C
z _C ”> z _C
It can be set as the structure which satisfies these. Although expressed as “x ₁ = x _C ”, this expression is not only strictly arithmetically equal,
0.90 ≦ x _C ″ / x ₁ ≦ 1.10
Is included.

In the electronic device having the 2-A configuration (or the electronic device having the 2-B configuration) including the above-described preferable configuration of the electronic device having the 2-A configuration (or the electronic device having the 2-B configuration) The crystal structure of the crystal constituting the interface layer of the second compound semiconductor layer (or the first compound semiconductor layer) can be a hexagonal system. In such a configuration, the laminated structure is made of a GaN-based compound semiconductor, and the contact layer has the same composition as the GaN-based compound semiconductor that forms the interface layer of the second compound semiconductor layer (or the first compound semiconductor layer). The GaN-based compound semiconductor may further include a GaN-based compound semiconductor containing oxygen atoms, or the stacked structure may be formed of a GaN-based compound semiconductor, and the contact layer may be a second compound. A GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the interface layer of the semiconductor layer (or the first compound semiconductor layer) can be used. In the latter case, specifically, the interface layer of the second compound semiconductor layer (or the first compound semiconductor layer) is composed of a GaN layer, and the contact layer is
_{_{(A) Al X Ga Y In}} Z N ( where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1) consisting of structure _{_{(b) Al X Ga Y In}} Z N S O _T (where X + Y + Z = 1, 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ Z ≦ 1, 0 <S ≦ 1, 0 <T ≦ 1) (c) Al _X Ga _Y In _Z N _{_S} P _{_1-S} (where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1,0 ≦ S <1) consisting of structure _{_{(d) Al X Ga Y In}} Z N _{_S} As _{_1-S} (where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1,0 ≦ S <1) consists _{_{(e) Al X Ga Y In}} Z N S Sb _1-S (where X + Y + Z = 1, 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ Z ≦ 1, 0 ≦ S <1) can be exemplified. Whether or not oxygen atoms are contained in the GaN-based compound semiconductor can be measured by, for example, an energy dispersive X-ray analysis method attached to a transmission electron microscope or a three-dimensional atom probe method.

Alternatively, the electronic device having the 2-A configuration or the electronic device having the 2-B configuration including the above-described various preferable configurations of the electronic device having the 2-A configuration or the electronic device having the 2-B configuration. The stacked structure may be made of a GaN-based compound semiconductor, and the contact layer may be made of one material selected from the group consisting of ZnO, ZnSe, CdO, CdS, and CdSe.

The electronic device having the 2-A configuration (or the configuration of the 2-B configuration) including the various preferred configurations described above of the electronic device having the 2-A configuration (or the electronic device having the 2-B configuration). In the electronic device), the value of the band gap energy of the compound semiconductor constituting the contact layer is smaller than the value of the band gap energy of the compound semiconductor constituting the interface layer of the second compound semiconductor layer (or the first compound semiconductor layer). It is preferable.

Further, the electronic device having the 2-A configuration or the second-B configuration including the various preferred configurations described above of the electronic device having the 2-A configuration or the electronic device having the 2-B configuration has been described. In the electronic device, the first conductivity type may be n-type, and the second conductivity type may be p-type.

As described above, in the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, the laminated structure and the contact layer are preferably formed of a GaN-based compound semiconductor. Examples of compound semiconductors constituting the second compound semiconductor layer other than the interface layer, the active layer, and the first compound semiconductor layer include GaN-based compound semiconductors such as GaN, AlGaN, InGaN, and AlInGaN, and constitute the active layer. Examples of the compound semiconductor to be used include InGaN and AlInGaN. Furthermore, these compound semiconductors may contain boron (B) atoms, thallium (Tl) atoms, arsenic (As) atoms, phosphorus (P) atoms, and antimony (Sb) atoms as desired. . Layered structure formation methods (film formation methods) include metalorganic chemical vapor deposition (MOCVD, MOVPE), metalorganic molecular beam epitaxy (MOMBE), and hydride gas in which halogen contributes to transport or reaction. Examples thereof include a phase growth method (HVPE method) and a plasma assisted physical vapor deposition method (PPD method). Here, trimethylgallium (TMG) and triethylgallium (TEG) can be mentioned as the organic gallium source in the MOCVD method, and ammonia gas and hydrazine can be mentioned as the nitrogen source. Further, when aluminum (Al) or indium (In) is contained as a constituent atom of the GaN-based compound semiconductor layer, trimethylaluminum (TMA) may be used as the Al source, and trimethylindium (TMI) may be used as the In source. Good. Furthermore, monosilane (SiH ₄ ) may be used as the Si source, and cyclopentadienyl magnesium, methylcyclopentadienyl magnesium, or biscyclopentadienyl magnesium (Cp ₂ Mg) may be used as the Mg source. In the case of forming a ridge stripe structure from a laminated structure composed of a first compound semiconductor layer, an active layer, and a second compound semiconductor layer, as a method of etching the laminated structure to form the ridge stripe structure, lithography technology and wet etching are used. A combination of technologies, a combination of lithography technology and dry etching technology can be mentioned. The configuration of the laminated structure itself can be a known configuration. The laminated structure is formed on an electronic device manufacturing substrate (hereinafter simply referred to as “manufacturing substrate”), and the first compound semiconductor layer, the active layer, and the second compound semiconductor layer are stacked from the manufacturing substrate side. Has a structured. As a method for forming a contact layer, in addition to the above-described stacked structure forming method, atomic layer deposition (ALD, Atomic Layer Deposition), migration enhanced epitaxy (MEE, Migration-Enhanced Epitaxy), pulsed laser Examples thereof include a deposition method (PLD method, Pulsed Laser Deposition method), a heat treatment method, and the like.

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, the active layer may be composed of a single compound semiconductor layer, a single quantum well structure (SQW structure), or It may have a multiple quantum well structure (MQW structure). An active layer having a quantum well structure has a structure in which at least one well layer and a barrier layer are stacked. However, as a combination of (a compound semiconductor constituting a well layer, a compound semiconductor constituting a barrier layer), InGaN, GaN), (InGaN, AlInGaN), and (InGaN, InGaN) [however, the composition of InGaN constituting the well layer and the composition of InGaN constituting the barrier layer are different]. Furthermore, the barrier layer may be composed of a layer group having a plurality of compositions.

In the electronic device having the 2-A configuration or the electronic device having the 2-B configuration, the first compound semiconductor layer is provided with the first conductivity type, and the second compound semiconductor layer and the contact layer are provided with the second conductivity type. For this purpose, impurities may be introduced into each of the first compound semiconductor layer, the second compound semiconductor layer, and the contact layer. Examples of n-type impurities added to the compound semiconductor layer include silicon (Si), sulfur (S), selenium (Se), germanium (Ge), tellurium (Te), tin (Sn), carbon (C), and titanium. (Ti), oxygen (O), palladium (Pd), and as p-type impurities, zinc (Zn), magnesium (Mg), carbon (C), beryllium (Be), cadmium (Cd), Calcium (Ca) and barium (Ba) can be mentioned.

In the electronic device having the configuration 2-A, the second electrode is in contact with the second compound semiconductor layer through the contact layer, while the first electrode is electrically connected to the first compound semiconductor layer. . That is, the first electrode is formed on the first compound semiconductor layer, or the first electrode is connected to the first compound semiconductor layer via the conductive material layer and the manufacturing substrate. In the electronic device having the configuration 2-B, the first electrode is in contact with the first compound semiconductor layer through the contact layer, while the second electrode is formed on the second compound semiconductor layer. . The second electrode may be in contact with the second compound semiconductor layer via the contact layer, and the first electrode may be in contact with the first compound semiconductor layer via the second contact layer. .

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, when the first conductivity type is n-type and the second conductivity type is p-type, the first electrode is, for example, gold (Au ), Silver (Ag), palladium (Pd), platinum (Pt), nickel (Ni), Al (aluminum), Ti (titanium), tungsten (W), vanadium (V), chromium (Cr), Cu (copper) ), Zn (zinc), tin (Sn), and indium (In), it is desirable to have at least one metal (including alloys) selected from the group consisting of single layer configuration or multilayer configuration, for example, Illustrate Ti / Au, Ti / Al, Ti / Pt / Au, Ti / Al / Au, Ti / Pt / Au, Ni / Au, Ni / Au / Pt, Ni / Pt, Pd / Pt, Ag / Pd be able to. In addition, the layer before “/” in the multilayer structure is located closer to the active layer side. The same applies to the following description.

Alternatively, in the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, when the first electrode is formed on the first compound semiconductor layer having the n-type conductivity type, You may comprise from a transparent conductive material layer. As described above, as the transparent conductive material constituting the transparent conductive material layer, the transparent conductive material containing indium atoms [specifically, indium oxide, indium tin oxide, Sn-doped ITO, In ₂ O ₃ , including crystalline ITO and amorphous ITO), indium zinc oxide (IZO), indium gallium oxide (IGO), indium doped gallium zinc oxide (IGZO, In -GaZnO ₄ ), IFO (F-doped In ₂ O ₃ )], tin oxide (SnO ₂ ), ATO (Sb-doped SnO ₂ ), FTO (F-doped SnO ₂ ), zinc oxide (Including ZnO, Al-doped ZnO, B-doped ZnO, and Ga-doped ZnO), antimony oxide, spinel oxide, YbFe ₂ O An oxide having a _four structure can be exemplified. Alternatively, as the first electrode and the second electrode, a transparent conductive material layer having a base layer of gallium oxide, titanium oxide, niobium oxide, nickel oxide, or the like can be given.

Alternatively, in the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, as a material having a good light transmittance and a small work function value constituting the first electrode, calcium (Ca), Alkaline earth metals such as barium (Ba), alkali metals such as lithium (Li) and cesium (Cs), indium (In), magnesium (Mg), silver (Ag), gold (Au), nickel (Ni), Gold-germanium (Au—Ge) and the like can also be mentioned. Furthermore, mention may be made of alkali metal oxides, alkali metal fluorides, alkaline earth metal oxides, alkaline earth fluorides such as Li ₂ O, Cs ₂ Co ₃ , Cs ₂ SO ₄ , MgF, LiF and CaF _2. You can also.

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, a pad electrode is provided on the first electrode or the second electrode so as to be electrically connected to an external electrode or a circuit. Also good. The pad electrode is at least one metal (including alloy) selected from the group consisting of Ti (titanium), aluminum (Al), Pt (platinum), Au (gold), Ni (nickel), and Pd (palladium). It is desirable to have a single layer configuration or a multi-layer configuration including Alternatively, the pad electrode may be a Ti / Pt / Au multilayer structure, a Ti / Au multilayer structure, a Ti / Pd / Au multilayer structure, a Ti / Pd / Au multilayer structure, a Ti / Ni / Au multilayer structure, A multi-layer structure exemplified by a multi-layer structure of Ti / Ni / Au / Cr / Au can also be used.

In the electronic device having the configuration 2-A or the electronic device having the configuration 2-B, the manufacturing substrate may be left, or the first compound semiconductor layer, the active layer, and the second compound may be left on the manufacturing substrate. After sequentially forming the semiconductor layer, the contact layer, the second electrode, etc., the manufacturing substrate may be removed. Specifically, the first compound semiconductor layer, the active layer, the second compound semiconductor layer, the contact layer, and the second electrode are sequentially formed on the manufacturing substrate, and the second electrode is fixed to the support substrate, and then the manufacturing substrate. And the first compound semiconductor layer may be exposed. The removal of the production substrate can be performed based on an etching method or a polishing method, or can be performed based on a chemical / mechanical polishing method (CMP method). First, alkaline aqueous solution such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, ammonia solution + hydrogen peroxide solution, sulfuric acid solution + hydrogen peroxide solution, hydrochloric acid solution + hydrogen peroxide solution, phosphoric acid solution + hydrogen peroxide solution A part of the manufacturing substrate is removed by a wet etching method using a dry etching method, a dry etching method, a lift-off method using a laser, a mechanical polishing method or the like, or a combination thereof. The first compound semiconductor layer may be exposed by reducing the thickness and then performing a chemical / mechanical polishing method. In this case, in the electronic device having the second-B configuration, the contact layer and the first electrode may be sequentially formed on the exposed first compound semiconductor layer.

The electronic device having the 2-A configuration or the electronic device having the 2-B configuration including the various preferable configurations described above of the electronic device having the 2-A configuration or the electronic device having the 2-B configuration In this case, the light generated in the active layer can be emitted to the outside from the end face (side surface) of the laminated structure, or can be emitted to the outside via the second compound semiconductor layer. It can also be set as the structure radiate | emitted outside through a 1st compound semiconductor layer. In an electronic device configured to emit light from the first compound semiconductor layer side, the manufacturing substrate may be removed as described above.

In addition to GaN substrates and sapphire substrates, GaAs substrates, SiC substrates, alumina substrates, ZnS substrates, ZnO substrates, AlN substrates, LiMgO substrates, LiGaO ₂ substrates, MgAl ₂ O ₄ substrates, InP substrates, Si as well as GaN substrates and sapphire substrates. Examples of the substrate include those having a base layer and a buffer layer formed on the surface (main surface) of these substrates. Mainly, when a GaN-based compound semiconductor layer is formed on a substrate, the GaN substrate is preferred because of its low defect density, but it is known that the characteristics of the GaN substrate change from polar / nonpolar / semipolar depending on the growth surface. ing.

Alternatively, as the production substrate, in addition to the above-mentioned various substrates, transparent inorganic substrates such as glass substrates and quartz substrates, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonate (PC) resins; Polyethersulfone (PES) resin; Polyolefin resin such as polystyrene, polyethylene, polypropylene; Polyphenylene sulfide resin; Polyvinylidene fluoride resin; Tetraacetyl cellulose resin; Brominated phenoxy resin; Aramid resin; Polyimide resin; Polystyrene resin; Polysulfone resin; Acrylic resin; Epoxy resin; Fluororesin; Silicone resin; Diacetate resin; Triacetate resin; Polyvinyl chloride resin; Mention may be made of a transparent plastic substrate or a film. Examples of the glass substrate include a soda glass substrate, a heat resistant glass substrate, and a quartz glass substrate.

The support substrate may be composed of various substrates such as a GaN substrate, a sapphire substrate, a GaAs substrate, an SiC substrate, an alumina substrate, a ZnS substrate, a ZnO substrate, a LiMgO substrate, a LiGaO ₂ substrate, an MgAl ₂ O ₄ substrate, and an InP substrate. Alternatively, an insulating substrate made of AlN or the like, a semiconductor substrate made of Si, SiC, Ge or the like, a metal substrate, or an alloy substrate can be used, but it is preferable to use a conductive substrate. Alternatively, it is preferable to use a metal substrate or an alloy substrate from the viewpoints of mechanical properties, elastic deformation, plastic deformability, heat dissipation, and the like. Examples of the thickness of the support substrate include 0.05 mm to 0.5 mm. As a method for fixing the second electrode to the support substrate, a known method such as a solder bonding method, a room temperature bonding method, a bonding method using an adhesive tape, a bonding method using wax bonding, or the like can be used. From the viewpoint of ensuring, it is desirable to employ a solder bonding method or a room temperature bonding method. For example, when a silicon semiconductor substrate which is a conductive substrate is used as a support substrate, it is desirable to employ a method capable of bonding at a low temperature of 400 ° C. or lower in order to suppress warping due to a difference in thermal expansion coefficient. When a GaN substrate is used as the support substrate, the bonding temperature may be 400 ° C. or higher.

In the electronic device having the 2-A configuration or the electronic device having the 2-B configuration including the various preferable configurations described above of the electronic device having the 2-A configuration or the electronic device having the 2-B configuration As an electronic device, a light emitting / receiving element, specifically, an edge emitting semiconductor laser element, an edge emitting superluminescent diode (SLD), a surface emitting laser element (also called vertical cavity laser, VCSEL) And a semiconductor light emitting device such as a light emitting diode (LED), a semiconductor optical amplifier, a solar cell, and a photosensor. A semiconductor optical amplifier amplifies in the state of direct light without converting an optical signal into an electrical signal, has a laser structure that eliminates the resonator effect as much as possible, and converts incident light based on the optical gain of the semiconductor optical amplifier. Amplify. In the semiconductor laser element, a resonator is configured by optimizing the light reflectance at the first end face and the light reflectance at the second end face, and light is emitted from the first end face. Alternatively, an external resonator may be arranged. On the other hand, in the superluminescent diode, the light reflectivity at the first end face is set to a very low value, the light reflectivity at the second end face is set to a very high value, and the active layer is formed without forming a resonator. The light generated in step 1 is reflected at the second end face and emitted from the first end face. In the semiconductor laser element and the super luminescent diode, a non-reflective coating layer (AR) or a low-reflective coating layer is formed on the first end surface, and a high-reflective coating layer (HR) is formed on the second end surface. Is formed. Further, in the semiconductor optical amplifier, the light reflectance at the first end face and the second end face is set to a very low value, and the light incident from the second end face is amplified without constituting the resonator, thereby the first end face. Emanates from. In the surface emitting laser element, laser oscillation is generated by resonating light between two light reflecting layers (Distributed Bragg Reflector layer, DBR layer).

Generally, a non-reflective coating layer (AR) or a low-reflective coating layer is formed on the light emitting end surface or the light incident end surface. Further, a highly reflective coating layer (HR) is formed on the light reflecting end face. As an antireflection coating layer (low reflection coating layer), at least 2 selected from the group consisting of a titanium oxide layer, a tantalum oxide layer, a zirconium oxide layer, a silicon oxide layer, an aluminum oxide layer, an aluminum nitride layer, and a silicon nitride layer The layered structure of a kind of layer can be mentioned, It can form based on PVD methods, such as sputtering method and a vacuum evaporation method.

Examples of the semiconductor laser element include, but are not limited to, a semiconductor laser element having a ridge stripe type separated confinement heterostructure (SCH structure, separate-confinement heterostructure). Alternatively, a semiconductor laser element having an oblique ridge stripe type separated confinement heterostructure can be cited. In other words, the axis of the semiconductor laser element and the axis of the ridge stripe structure can intersect at a predetermined angle. Here, examples of the predetermined angle φ include 0.1 degrees ≦ φ ≦ 10 degrees. The axis of the ridge stripe structure is a straight line connecting the bisectors at both ends of the ridge stripe structure at the light emitting end face and the bisectors at both ends of the ridge stripe structure at the light reflecting end face. The axis of the semiconductor laser element refers to an axis perpendicular to the virtual vertical plane at the light emitting end face and the virtual vertical plane at the light reflecting end face. The planar shape of the ridge stripe structure may be linear or curved. Alternatively, a tapered (flared) ridge stripe type (for example, a structure that is monotonously and gradually widened in a tapered shape from the light emitting end face toward the light reflecting end face, from the light emitting end face toward the light reflecting end face, First, a semiconductor laser device having a separate confinement heterostructure (including a configuration in which it is first widened and exceeds a maximum width and then narrowed) can be given. The ridge stripe structure may be composed of a part of the second compound semiconductor layer in the thickness direction, may be composed of the second compound semiconductor layer and the active layer, or may be composed of the second compound semiconductor layer, the active layer You may be comprised from the layer and a part of thickness direction of the 1st compound semiconductor layer. However, the semiconductor laser element is not limited to these structures. Other semiconductor laser elements include semiconductor laser elements with an index guide structure, bi-section type with a light emitting region and a saturable absorption region juxtaposed in the cavity direction, and multi-section type (multi-electrode type). Semiconductor laser element, SAL (Saturable Absorber Layer) type in which light emitting region and saturable absorption region are arranged in the vertical direction, or WI (Weakly Index Guide) type semiconductor laser in which saturable absorption region is provided along a ridge stripe structure An element can also be mentioned.

The first electrode, the second electrode, and the insulating layer are formed on the basis of the sputtering method. Specific examples include a magnetron sputtering method and a parallel parallel plate sputtering method, and a plasma using a DC discharge method or an RF discharge method. There may be mentioned those using the generation method. Alternatively, as a method of forming the first electrode, depending on the material constituting the first electrode, a vacuum deposition method, a reactive deposition method, an electron beam deposition method, an ion plating method, a PVD method, a pyrosol method, an organic method, etc. Examples include a method of thermally decomposing a metal compound, a spray method, a dipping method, and various CVD methods including an MOCVD method, an electroless plating method, and an electrolytic plating method. The preferred configuration of the present disclosure has a great feature that the work function can be controlled by the oxygen flow rate (oxygen gas partial pressure, oxygen gas introduction amount).

In addition to an imaging device (solid-state imaging device) such as a TV camera, an optical sensor or an image sensor can be configured by the electronic device of the present disclosure.

Further, the electronic device having the configuration 2-A or the electronic device having the configuration 2-B can be applied to a display device, for example. That is, as such a display device, a projector device, an image display device, a monitor device, or the like, which has an electronic device having the configuration 2-A or an electronic device having the configuration 2-B as a light source. Examples thereof include a reflective liquid crystal display device including an electronic device or an electronic device having a configuration 2-B as a light source, a head-mounted display (HMD), a head-up display (HUD), and various types of illumination. Further, an electronic device having the configuration 2-A or an electronic device having the configuration 2-B can be used as a light source of the microscope. However, the application field of the electronic device having the configuration 2-A or the electronic device having the configuration 2-B is not limited thereto.

Example 1 relates to an electronic device of the present disclosure, a manufacturing method thereof, an insulating material of the present disclosure, and further relates to an electronic device having a first-C configuration. A schematic cross-sectional view of the electronic device of Example 1 is shown in FIG. 1A. The electronic device of Example 1 constitutes a photoelectric conversion element.

The electronic device of Example 1 or Examples 2 to 6 described later includes a light emitting / receiving layer 20,

first electrodes

31 and 91 electrically connected to the light emitting / receiving layer 20, and the light emitting / receiving layer 20.

Second electrodes

32 and 92 formed thereon are provided. The

second electrodes

32 and 92 are composed of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O). That is, it consists of a conductive amorphous oxide. The light emitting / receiving layer 20 includes an insulating layer 40 made of at least a quaternary compound of indium (In), gallium (Ga) and / or aluminum (Al), zinc (Zn), and oxygen (O). , 80. That is, the insulating

layers

40 and 80 are also made of an insulating amorphous oxide. The composition ratio of oxygen (O) in the insulating

layers

40 and 80 is higher than the composition ratio of oxygen (O) in the

second electrodes

32 and 92. The insulating material of Example 1 (specifically, the material constituting the insulating layers 40 and 80) is indium (In), gallium (Ga) and / or aluminum (Al), and zinc (Zn). And at least a quaternary compound with oxygen (O). That is, the insulating material is also made of an insulating amorphous oxide.

More specifically, in the electronic devices of Example 1 or Examples 2 to 6 described later, the insulating

layers

40 and 80 and the

second electrodes

32 and 92 are made of indium-doped gallium-zinc oxide (IGZO, It is made of a transparent conductive material such as In—GaZnO ₄ ). That is, the

second electrodes

32 and 92 are made of In _a (Ga, Al) _b Zn _c O _d , and the insulating

layers

40 and 80 are In _a (Ga, Al) _b Zn _c O _e (where d <e ). Note that “a”, “b”, “c”, “d”, and “e” can take various values. The

second electrodes

32 and 92 and the insulating

layers

40 and 80 are made of indium-doped gallium-zinc oxide (IGZO), indium-gallium oxide (IGO), aluminum oxide-doped zinc oxide (AZO). , Indium-zinc oxide (IZO), or gallium-doped zinc oxide (GZO). The value of “a” is 0.05 to 0.10, the value of “b” is 0.10 to 0.20, the value of “c” is 0.10 to 0.20, and the value of “d” is Examples of the values of 0.30 to 0.40 and “e” are 0.45 to 0.60, but are not limited to these values.

In the electronic device 10 of the first embodiment, the first electrode 31 is made of a transparent conductive material such as indium-tin oxide (ITO), and the light emitting / receiving layer 20 is an organic photoelectric conversion material, specifically, Is made of, for example, quinacridone having a thickness of 0.1 μm. The light emitting / receiving layer 20 is sandwiched between the first electrode 31 and the second electrode 32. That is, the first electrode 31, the light emitting / receiving layer 20, and the second electrode 32 are laminated in this order. More specifically, in the electronic device 10 according to the first embodiment, the second electrode 31 is formed on the substrate 11 made of a silicon semiconductor substrate, and the light emitting / receiving layer 20 is formed on the first electrode 31. The second electrode 32 is formed on the light emitting / receiving layer 20. That is, the electronic device 10 of Example 1 or Examples 2 to 3 described later has a two-terminal electronic device structure including the first electrode 31 and the second electrode 32. Specifically, photoelectric conversion is performed in the light emitting / receiving layer 20. That is, the electronic device 10 according to the first embodiment or the second to third embodiments described later includes a photoelectric conversion element. In addition, examples of the material constituting the first electrode 31 include transparent conductive materials such as indium-zinc oxide (IZO) and tin oxide (SnO ₂ ).

Furthermore, the light transmittance of the insulating

layers

40 and 80 with respect to light with a wavelength of 400 nm to 660 nm is 80% or more, specifically, 90% with respect to light with a wavelength of 550 nm, and the second electrode 32 with respect to light with a wavelength of 400 nm to 660 nm. , 92 has a light transmittance of 75% or more, specifically, 85% for light having a wavelength of 550 nm. The light transmittance of the

first electrodes

31, 91, the

second electrodes

32, 92, and the insulating

layers

40, 80 is such that the

first electrodes

31, 91, the

second electrodes

32, 92, and the insulating layer are formed on a transparent glass plate. It can be measured by forming a film. The sheet resistance values of the

second electrodes

32 and 92 are 3 × 10 Ω / □ to 1 × 10 ³ Ω / □, specifically 8 × 10 Ω / □. Furthermore, the sheet resistance values of the insulating

layers

40 and 80 are 2 × 10 ⁵ Ω / □ to 5 × 10 ⁶ Ω / □, specifically,
8 × 10 ⁵ Ω / □ (Example 1A below)
4 × 10 ⁶ Ω / □ (Example 1B below)
It is.

An IGZO film was formed at room temperature (specifically, 22 ° C. to 28 ° C.) based on a sputtering method. And when the relationship between the oxygen gas partial pressure at the time of film-forming and the electroconductivity and insulation of the obtained IGZO film was investigated, it became as shown in Table 1 below. Further, FIG. 2 shows the result of examining the relationship between the oxygen gas partial pressure during film formation and the internal stress of the obtained IGZO film. A parallel parallel plate sputtering apparatus or a DC magnetron sputtering apparatus was used as the sputtering apparatus, argon (Ar) gas was used as the process gas, and an InGaZnO ₄ sintered body was used as the target. The same applies to the formation of the

second electrodes

32 and 92 and the insulating

layers

40 and 80 described below. The internal stress was measured based on a well-known method using a commercially available thin film stress measuring device. In addition, each sample, which was formed on a Si wafer and subjected to stress measurement, was immersed in acetone for 30 seconds, and then the state of the insulating layer was observed using an optical microscope (5 times magnification). The result is shown in the column of “peeled state” in Table 2 below. In the results of the immersion test, the case where there was no change in the insulating layer before and after immersion was designated as “no peeling”, and the case where even a part of the insulating layer was peeled was designated as “with peeling”.

[Table 1]
Oxygen gas partial pressure 0.003 Pa or less Conductivity 0.004 Pa to 0.02 Pa Semiconductor 0.04 Pa or more Insulative

Further, the configuration of the insulating layer 40 made of the IGZO film, the internal stress, and the peeling state of the insulating layer 40 from the second electrode 32 were examined. The results are shown in Table 2 below. In Comparative Example 1, the insulating layer was made of SiON formed based on the sputtering method.

[Table 2]
Insulating layer thickness Internal stress (compressive stress) Peeling state Example 1A 100 nm 65 MPa No peeling Example 1B 100 nm 24 MPa No peeling Comparative Example 1 200 nm 200 MPa With peeling

Also, from various test results, it was found that the internal stress of the insulating

layers

40 and 80 is preferably a compressive stress of 10 MPa to 90 MPa. For this purpose, in order to control conductivity and insulation, oxygen gas partial pressure (oxygen gas introduction amount) when the

second electrodes

32 and 92 and the insulating

layers

40 and 80 are formed by sputtering is used. ) Is preferably controlled to control the composition ratio of oxygen (O) in the

second electrodes

32 and 92 and the insulating

layers

40 and 80. That is, it was found that the oxygen gas partial pressure is preferably 0.04 Pa to 0.15 Pa when forming the insulating

layers

40 and 80.

Hereinafter, a method for manufacturing the electronic device of Example 1 will be described. In addition, the electrode obtained by the manufacturing method (electrode formation method in an electronic device) of the electronic device of Example 1 is an electrode for a photoelectric conversion element. The electronic device 10 obtained in the manufacturing method of the electronic device of Example 1 constitutes a photoelectric conversion element.

[Step-100]
A substrate 11 made of a silicon semiconductor substrate is prepared. Here, for example, an electronic device drive circuit (not shown) and wiring 12 are provided on the substrate 11, and an interlayer insulating film 13 is formed on the surface. The interlayer insulating film 13 is provided with an opening 14 where the wiring 12 is exposed at the bottom. Then, a first electrode 31 made of ITO is formed (film formation) on the interlayer insulating film 13 including the inside of the opening 14 based on a sputtering method.

[Step-110]
Next, after patterning the first electrode 31, the light emitting / receiving layer 20 made of quinacridone is formed (film formation) on the entire surface by vacuum deposition.

[Step-120]
Thereafter, a second electrode 32 made of a conductive amorphous oxide (specifically, made of IGZO) is formed on the light emitting / receiving layer 20 based on a sputtering method, and then the second electrode 32 is formed as desired. Patterning is performed based on a well-known patterning technique. Next, the insulating layer 40 is formed (film formation) on the entire surface by changing the sputtering conditions. That is, the light emitting / receiving layer 20 is covered with the insulating layer 40 made of an insulating amorphous oxide (specifically, made of IGZO) based on a sputtering method. Thus, the electronic device of Example 1 having the structure shown in FIG. 1A can be obtained.

Alternatively, after the insulating layer 40 made of an insulating amorphous oxide (specifically, made of IGZO) is formed on the light emitting / receiving layer 20 based on the sputtering method, the second electrode 32 is formed. The portion of the insulating layer 40 to be removed is removed based on a known patterning technique. Next, after changing the sputtering conditions to form the second electrode 32 made of a conductive amorphous oxide (specifically, made of IGZO) on the entire surface, the second electrode 32 is formed into a desired shape. Patterning is performed based on a known patterning technique. Thus, the electronic device of Example 1 having the structure shown in FIG. 1B can be obtained. That is, the insulating layer 40 may be formed on the upper side of the second electrode 32 or may be formed on the lower side.

In addition, by controlling the oxygen gas partial pressure (oxygen gas introduction amount) when forming the second electrode 32 and the insulating layer 40 based on the sputtering method, that is, when forming the second electrode 32 based on the sputtering method. By increasing the oxygen gas partial pressure (oxygen gas introduction amount) at the time of forming the insulating layer 40 rather than the oxygen gas partial pressure (oxygen gas introduction amount), the composition ratio of oxygen (O) in the insulating layer 40 is increased. The composition ratio is higher than the oxygen (O) composition ratio in the two electrodes 32. The oxygen gas partial pressure when forming the insulating layer 40 based on the sputtering method is set to 0.04 Pa to 0.15 Pa. Further, the temperature at which the second electrode 32 and the insulating layer 40 are formed based on the sputtering method is set to room temperature, specifically 22 ° C. to 28 ° C. A parallel parallel plate sputtering apparatus or a DC magnetron sputtering apparatus was used as the sputtering apparatus, argon (Ar) gas was used as the process gas, and an InGaZnO ₄ sintered body was used as the target.

As described above, in Example 1, the composition of the second electrode and the insulating layer and the composition ratio of oxygen are defined, and the second electrode and the insulating layer can be formed of the same material. An electronic device can be manufactured by a typical method, and although the second electrode and the insulating layer are made of the same material, conductivity and insulation can be imparted to each of them. Moreover, since the electronic device can be manufactured at a lower temperature process, it is possible to prevent thermal degradation of the light emitting / receiving layer, and furthermore, the film stress of the insulating layer can be suppressed, which is high. An electronic device having reliability can be provided.

Example 2 is a modification of Example 1, and relates to an electronic device having a first-A configuration and an electronic device having a first-C configuration. That is, in the electronic device of Example 2, the light emitting / receiving layer 20 is sandwiched between the first electrode 31 and the second electrode 32, and the work function value of the second electrode 32 and the work function of the first electrode 31 are The difference from the value is 0.4 eV or more. Here, the difference between the work function value of the second electrode 32 and the work function value of the first electrode 31 is set to 0.4 eV or more, so that the inside of the light emitting / receiving layer 20 is based on the difference of the work function values. Generate an electric field to improve internal quantum efficiency. The second electrode 32 functions as a cathode electrode (cathode). That is, it functions as an electrode for extracting electrons. On the other hand, the first electrode 31 functions as an anode electrode (anode). That is, it functions as an electrode for extracting holes. Here, the work function of IGZO constituting the second electrode 32 is 4.1 eV to 4.2 eV although it depends on the film forming conditions. In addition, the work function of ITO constituting the first electrode 31 is 4.8 eV to 5.0 eV as an example, although it depends on the film forming conditions.

Specifically, the work function value of the second electrode 32 is controlled by controlling the oxygen gas introduction amount (oxygen gas partial pressure) when forming the second electrode 32 based on the sputtering method. An example of the result of obtaining the relationship between the oxygen gas partial pressure and the work function value of the second electrode 32 is shown in the graph of FIG. 3A. As the oxygen gas partial pressure value increases, that is, oxygen deficiency decreases. As the work function value of the second electrode 32 increases and the oxygen gas partial pressure value decreases, that is, as the oxygen deficiency increases, the work function value of the second electrode 32 decreases.

Thus, in the electronic device of Example 2, the work of the second electrode 32 is controlled by controlling the oxygen gas introduction amount (oxygen gas partial pressure) when forming the second electrode 32 based on the sputtering method. The function value is controlled. In the second electrode 32, the oxygen content is lower than the oxygen content of the stoichiometric composition.

FIG. 3B shows IV curves obtained in the electronic device (photoelectric conversion element) of Example 2 and the electronic device (photoelectric conversion element) of Comparative Example 2. In FIG. 3B, “A” is the measurement result of the electronic device of Example 2, “B” is the measurement result of the electronic device of Example 3 described later, and “C” is Comparative Example 2. It is a measurement result of the electronic device. Here, in the electronic device of Comparative Example 2, the second electrode 32 of the electronic device of Example 2 is made of ITO instead of IGZO. From FIG. 3B, it can be seen that in the electronic device of Example 2 or Example 3 to be described later, the current value increases abruptly at a reverse bias voltage of less than 1 volt (bias voltage of less than −1 volt). The values of internal quantum efficiency and on / off ratio of the electronic devices of Example 2 and Comparative Example 2 were as shown in Table 3 below. The internal quantum efficiency η is a ratio of the number of generated electrons to the number of incident photons, and can be expressed by the following equation.

η = {(h · c) / (q · λ)} (I / P) = (1.24 / λ) (I / P)
here,
h: Planck's constant c: speed of light q: charge of electron λ: wavelength of incident light (μm)
I: Bright current. In the measurement of Example 1, the current value (ampere / cm ² ) obtained at a reverse bias voltage of 1 volt
P: power of incident light (ampere / cm ² )
It is.

[Table 3]
Internal quantum efficiency (%) On / off ratio Example 2 39 2.6
Example 3 55 3.4
Comparative Example 2 5.4 1.4

In the electronic device of Comparative Example 2, since both the first electrode and the second electrode are made of ITO, a conceptual diagram of an energy diagram is shown in FIG. There is no difference from the work function value of the first electrode. Therefore, the holes from the second electrode easily flow into the first electrode, and as a result, the dark current increases. In addition, since there is no difference between the work function value of the second electrode and the work function value of the first electrode, there is no potential gradient when taking out electrons and holes (that is, the internal electric field in the light emitting / receiving layer). Therefore, it is difficult to smoothly extract electrons and holes (see the conceptual diagram in FIG. 4D). On the other hand, in the electronic device of Example 2, the second electrode is made of IGZO, the first electrode is made of ITO, the work function value of the second electrode and the work function value of the first electrode. Is 0.4 eV or more. A conceptual diagram of the energy diagram is shown in FIG. 4A. Accordingly, it is possible to prevent holes from the first electrode from flowing into the second electrode, and as a result, generation of dark current can be suppressed. In addition, since the difference between the work function value of the second electrode and the work function value of the first electrode is 0.4 eV or more, a potential gradient is generated when electrons and holes are taken out (that is, the light emitting / receiving layer). In this case, an internal electric field is generated), and this potential gradient can be applied to smoothly extract electrons and holes (see the conceptual diagram in FIG. 4C).

Furthermore, the result of investigating the correlation between the internal quantum efficiency and the difference between the work function values is shown in the graph of FIG. 5A, and light is irradiated at a dark current (in the measurement of Example 2, at a reverse bias voltage of 1 volt). The graph of FIG. 5B shows the result of examining the correlation between the current value obtained when not) and the difference between the work function values. 5A and 5B indicate the difference between the work function value of the second electrode 32 and the work function value of the first electrode 31, and the horizontal axes of FIGS. A difference between the work function value of the second B layer 32B of the two electrodes 32 and the work function value of the second A layer 32A of the second electrode 32 is shown. From FIG. 5A and FIG. 5B, a clear increase in internal quantum efficiency and a clear decrease in dark current were recognized when the difference in work function value was around 0.4 eV.

As described above, in the electronic device of Example 2, since the difference between the work function value of the second electrode and the work function value of the first electrode is defined, the first electrode and the second electrode are defined. When a bias voltage (more specifically, a reverse bias voltage) is applied between the two, a large internal electric field can be generated in the light emitting / receiving layer based on the difference in the work function value. The improvement can be achieved, that is, the photocurrent can be increased, and the generation of dark current can be suppressed. In the electronic device manufacturing method (second electrode forming method) of Example 2, the work of the second electrode is controlled by controlling the oxygen gas introduction amount (oxygen gas partial pressure) when forming based on the sputtering method. As a result of controlling the function value, it is possible to generate a large internal electric field in the light emitting / receiving layer based on the difference in the work function value, so that the internal quantum efficiency can be improved. An electronic device capable of increasing current and suppressing generation of dark current can be manufactured by a simple manufacturing process.

Example 3 is a modification of Example 2, and relates to an electronic device having a first-B configuration and an electronic device having a first-C configuration. That is, in the electronic device of Example 3, the light emitting / receiving layer 20 is sandwiched between the first electrode 31 and the second electrode 32, and the second electrode 32 extends from the light emitting / receiving layer 20 side to the second B layer 32 </ b> B. In addition, the work function value of the second A layer 32A of the second electrode 32 is lower than the work function value of the second B layer 32B of the second electrode 32. A schematic partial cross-sectional view of the electronic device of Example 3 is shown in FIG. 1C.

Specifically, the difference between the work function value of the second A layer 32A of the second electrode 32 and the work function value of the second B layer 32B of the second electrode 32 is 0.1 eV to 0.2 eV, more specifically. Is 0.15 eV, and the difference between the work function value of the first electrode 31 and the work function value of the second A layer 32A of the second electrode 32 is 0.4 eV or more. The thickness of the second electrode 32 is 1 × 10 ⁻⁸ m to 1 × 10 ⁻⁷ m, specifically 50 nm. The thickness of the second A layer 32A of the second electrode 32 and the second electrode 32 are the same. The thickness ratio of the second B layer 32B is 9/1 to 1/9, specifically 9/1. Even in the third embodiment, by setting the difference between the work function value of the first electrode 31 and the work function value of the second A layer 32A of the second electrode 32 to 0.4 eV or more, the work function value Based on the difference, an internal electric field is generated in the light emitting / receiving layer to improve internal quantum efficiency. Here, when the composition of the second A layer 32A is In _a (Ga, Al) _b Zn _c O _d and the composition of the second B layer 32B is In _{a ′} (Ga, Al) _{b ′} Zn _{c ′} O _{d ′.} , A = a ′, b = b ′, c = c ′, and d <d ′. The values of the internal quantum efficiency and the on / off ratio of the electronic device of Example 3 are shown in Table 3 above. Further, FIG. 3B shows an IV curve obtained in the electronic device (photoelectric conversion element) of Example 3. Furthermore, the result of investigating the correlation between the internal quantum efficiency and the difference between the work function values is shown in the graph of FIG. 6A. Light is irradiated at a reverse bias voltage of 1 volt even in the measurement of Example 3. 6B shows the result of examining the correlation between the difference between the current value obtained when not) and the work function value. 6A and 6B, as the difference between the work function value of the second A layer of the second electrode and the work function value of the second B layer of the second electrode increases to about 0.2 eV, the internal quantum efficiency is increased. A clear increase and a clear decrease in dark current were observed.

In the manufacturing method of the electronic device of Example 3 (electrode formation method in the electronic device), in the same step as [Step-120] of Example 1, for example, as shown in the graph of FIG. By controlling the amount of oxygen gas introduced when forming based on the method, the work function values of the second A layer 32A and the second B layer 32B of the second electrode 32 are controlled.

In the electronic device of Example 3, the second electrode is composed of the second A layer and the second B layer, and the difference in work function between the second A layer and the second B layer is defined. The work function can be optimized, and the transfer (movement) of the carrier becomes easier.

Example 4 is a modification of Example 1 and relates to an electronic device having a configuration of 2-A. 7A and 7B are schematic partial cross-sectional views of the electronic device of Example 4. FIG. FIG. 7A is a schematic partial cross-sectional view along the arrow AA in FIG. 7B, in which the electronic device is cut along a virtual plane perpendicular to the extending direction of the waveguide structure (resonator structure). It is a typical partial sectional view at the time. FIG. 7B is a schematic partial cross-sectional view along the arrow BB in FIG. 7A, in which the electronic device is cut along a virtual plane parallel to the extending direction of the waveguide structure (resonator structure). It is a typical partial sectional view at the time.

In the electronic device of Example 4 or Examples 5 to 6 to be described later, the light emitting / receiving layer 20 includes the first compound semiconductor layer 71 having the first conductivity type, the active layer 73, and the first conductivity type. It consists of the laminated structure 70 which consists of the 2nd compound semiconductor layer 72 which has a different 2nd conductivity type. Specifically, the electronic device of Example 4 or Example 5 to Example 6 to be described later is composed of a semiconductor laser element, more specifically, a semiconductor laser element having a ridge stripe type separated confinement heterostructure. Yes. The first conductivity type is n-type, and the second conductivity type is p-type. That is, the electronic devices of Example 4 or Examples 5 to 6 described later include a first compound semiconductor layer 71 having an first conductivity type (specifically, an n-type in the example), an active layer 73, In addition, the stacked structure 70 (the light emitting / receiving layer 20) including the second compound semiconductor layer 72 having a second conductivity type (specifically, p-type in the embodiment) different from the first conductivity type is provided.

In the electronic device of Example 4, the second electrode 92 is formed on the second compound semiconductor layer 72 via the contact layer 74, and the thickness of the contact layer 74 is 4 atomic layers or less. Is the thickness. In addition, the interface between the contact layer 74 and the second compound semiconductor layer 72 is the xy plane, and the lattice constant (specifically) along the x-axis of the crystal constituting the interface layer 72A that is the portion of the second compound semiconductor layer 72 in contact with the contact layer 74 Specifically, the lattice constant along the a-axis) is x ₂ , the lattice constant along the z-axis (specifically, the lattice constant along the c-axis) is z ₂ , and the crystal constituting the contact layer 74 is 1 The length of the unit along the x-axis (specifically, the length along the a-axis) is x _C ', and the length along the z-axis (specifically, the length along the c-axis) z _C '
(Z _C '/ x _C ')> (z ₂ / x ₂ )
Satisfied.

In the electronic device of Example 4 or Examples 5 to 6 to be described later, the ridge stripe structure 60 is formed from a laminated structure 70 in which a first compound semiconductor layer 71, an active layer 73, and a second compound semiconductor layer 72 are laminated. And has a first end face 61 that emits light and a second end face 62 that faces the first end face 61. In the illustrated example, the planar shape of the ridge stripe structure 60 is linear. The ridge stripe structure 60 is formed by partially etching the second compound semiconductor layer 72 in the thickness direction. The region of the active layer 73 below the ridge stripe structure 60 corresponds to a light emitting region (current injection region). A high reflection coat layer (HR) is formed on the light emitting end face (first end face) 61 and the light reflecting end face (second end face), but the illustration of these coat layers is omitted. The light reflectance of the light emitting end face (first end face) 61 is lower than the light reflectance of the light reflecting end face (second end face) 62. The ridge stripe structure 60 and both sides thereof are covered with the insulating layer 80 described in the first embodiment. The portion of the insulating layer 80 on the top surface of the contact layer 74 (second compound semiconductor layer 72 in Example 6 described later) has been removed, and the contact layer 74 (second compound in Example 6 described later). A second electrode 92 is formed on the top surface of the semiconductor layer 72). Here, in the electronic device of the fourth embodiment, the second electrode 92 is made of the material described in the first embodiment. The second electrode 92 and the insulating layer 80 are formed by the same method as described in the first embodiment. A first electrode 91 formed by stacking a Ti layer / Pt layer / Au layer is formed on the back surface (the surface facing the main surface) of the GaN substrate 51.

Here, in the electronic device of Example 4, the crystal structure of the crystal composing the interface layer 72A of the second compound semiconductor layer 72 is hexagonal, and the crystal structure of the crystal composing the contact layer 74 is also hexagonal. is there. The stacked structure 70 is made of a GaN-based compound semiconductor, and the contact layer 74 is a GaN-based compound semiconductor having the same composition as that of the GaN-based compound semiconductor constituting the interface layer 72A of the second compound semiconductor layer 72, and GaN-based compound semiconductor containing oxygen atoms. The specific structure of the laminated structure 70 is shown in Table 4 below, and the compound semiconductor layer described at the bottom is formed on a GaN substrate 51 made of an n-type GaN substrate. The composition of the contact layer 74 is expressed as “p-type GaN (O)”, which indicates that the contact layer 74 is made of GaN containing oxygen atoms. The active layer 73 has a quantum well structure in which a well layer made of an InGaN layer and a barrier layer made of a GaN layer are stacked. Silicon (Si), oxygen (O), or germanium (Ge) is added to the GaN substrate 51 as an n-type impurity. The electronic device having the composition shown in Table 4 emits green light. That is, the emission wavelength of the electronic device of Example 4 is not less than 440 nm and not more than 600 nm, more specifically, not less than 495 nm and not more than 570 nm. The interface layer 72A in the second compound semiconductor layer 72 is made of p-type GaN having a thickness of 2.5 nm constituting the second cladding layer having a superlattice structure. In the second cladding layer, only one of the p-type AlGaN layer or the p-type GaN layer may have a modulation doping structure. Further, the first cladding layer and the second cladding layer can be composed of a quaternary InAlGaN layer as will be described later. An electronic device that emits blue light can be obtained by changing the composition.

[Table 4]

Hereinafter, the outline of the manufacturing method of the electronic device of Example 4 will be described.

[Step-400]
For example, a GaN substrate 51 having a c-plane that is a {0001} plane as a main surface is prepared. However, the main surface of the GaN substrate 51 is not limited to the c-plane which is a polar surface. Non-polar surfaces such as the {11-20} plane A, the {1-100} plane M, the {1-102} plane, or the {11-24} plane or the {11-22} plane A GaN substrate 51 having a semipolar plane such as a {11-2n} plane, a {10-11} plane, and a {10-12} plane as a main plane can also be used. First, the main surface of the GaN substrate 51 is cleaned by thermal cleaning or the like. Next, the buffer layer 52 is crystal-grown on the main surface of the GaN substrate 51 based on the MOCVD method. Subsequently, after the first cladding layer is grown, a first guide layer, an active layer, a second guide layer, an electron barrier layer, and a second cladding layer are sequentially formed. Thereafter, the contact layer 34 is formed based on the ALD method to obtain the contact layer 34 made of p-type GaN (O). The contact layer 34 is formed on the interface layer 32A made of p-type GaN having a thickness of 2.5 nm. The method for forming the contact layer 34 is not limited to the ALD method.

[Step-410]
Next, an etching mask is formed on the second compound semiconductor layer 72 (specifically, the contact layer 74), and the second compound semiconductor layer 72 is formed using the etching mask, for example, based on the RIE method. The ridge stripe structure 60 is formed by etching partly in the thickness direction, and then the etching mask is removed. The second compound semiconductor layer 72 and the active layer 73 may be etched in the thickness direction, or the second compound semiconductor layer 72, the active layer 73, and the first compound semiconductor layer 71 are partially etched in the thickness direction. May be.

[Step-420]
Thereafter, in the same manner as in [Step-120] in Example 1, an insulating layer 80 is formed on the entire surface, and then the insulating layer located on the top surface of the second compound semiconductor layer 72 (specifically, the contact layer 74) is formed. Part of layer 80 is removed. Then, the second electrode 92 is formed on the exposed second compound semiconductor layer 72 (specifically, the contact layer 74) in the same manner as in [Step-120] of the first embodiment. In addition, the first electrode 91 is formed on the back surface of the GaN substrate 51 after, for example, lapping and polishing the back surface side of the GaN substrate 51 to reduce the thickness of the GaN substrate 51 to about 100 μm.

[Step-430]
Next, the light emitting end face (first end face) 61 and the light reflecting end face (second end face) 62 are formed by cleaving the laminated structure 70. Thereafter, in order to connect the electrode to an external circuit or the like, a terminal or the like is formed based on a known method, and packaged or sealed, thereby completing the electronic device of Example 4.

In [Step-420], the second electrode 92 is formed on the entire surface in the same manner as in [Step-120] in Example 1. Then, the second electrode 92 is patterned, and then the insulating layer 80 is formed on the entire surface. After the formation, part of the second electrode 92 may be exposed by patterning the insulating layer 80. In this way, the structure shown in FIG. 8 can be obtained. That is, the insulating layer 80 may be formed on the upper side of the second electrode 92 or may be formed on the lower side.

A scanning transmission electron microscope image of the obtained electronic device is shown in FIG. The length along the x-axis (specifically, the length along the a-axis) in one unit of the crystal constituting the contact layer 74 measured from the scanning transmission electron microscope image is along x _C ′ and z-axis. Z _c ′ (specifically, the length along the c-axis) is
x _C '/2=0.17 nm
z _C '/2=0.31 nm
Met. On the other hand, the lattice constant (specifically, the lattice constant along the a axis) of the crystal constituting the interface layer 72A is x ₂ , and the lattice constant along the z axis (specifically, the c axis). Z ₂ is the lattice constant along
x _2/2 = 0.17nm
z _2/2 = 0.27nm
Met. That is,
(Z _C '/ x _C ')> (z ₂ / x ₂ )
Is satisfied. In addition, the contact layer 74 is pseudo-lattice matched with the interface layer 72 A of the second compound semiconductor layer 72. That is, when the lattice constant along the x axis of the crystal constituting the contact layer 74 is x _C and the lattice constant along the z axis is z _C ,
x ₂ = x _C '<x _C
z _C '> z _C
Is satisfied.

FIG. 10 is a graph showing the relationship between the series resistance value of the electronic device having the structure shown in FIGS. 7A and 7B and the work function value of the material constituting the second electrode 92 (p-side electrode). Regarding Ti, Ni / Au, and Pd, a series when a second electrode made of Ti, Ni / Au, or Pd is formed on a second cladding layer made of a p-type GaN layer, as in a conventional semiconductor laser device. Resistance value. There is a correlation between the series resistance value and the work function value. On the other hand, when the contact layer 74 of Example 4 is formed, that is, the contact layer 74 having a thickness of two atomic layers is provided between the interface layer 72A made of p-type GaN and the second electrode 92 made of ITO. In this case, the actual series resistance value is about 2/3 of the series resistance value estimated from the work function value of ITO (for example, 4.8 eV to 5.0 eV, depending on the film formation conditions). It is getting smaller. The drive voltage of the electronic device can be reduced by reducing the series resistance value, that is, the contact resistance value.

As described above, in the electronic device of Example 4, the lattice constant in the interface layer, which is the portion of the second compound semiconductor layer in contact with the contact layer, and the length in one unit of the crystal constituting the contact layer are predetermined. Therefore, a kind of distortion occurs in the contact layer. As a result, not only can the drive voltage be reduced, but also, for example, a material having a low work function value such as ITO can be used. It becomes possible to constitute the electrode, and the degree of freedom of selection of the material constituting the second electrode can be improved.

The fifth embodiment is a modification of the fourth embodiment. In Example 5, the laminated structure 70 is made of a GaN-based compound semiconductor, and the contact layer 74 is made of a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the interface layer 72A of the second compound semiconductor layer 72. . Alternatively, the laminated structure 70 is made of a GaN-based compound semiconductor, and the contact layer 74 is made of one kind of material selected from the group consisting of ZnO, ZnSe, CdO, CdS, and CdSe. The band gap energy value of the compound semiconductor constituting the contact layer 74 is smaller than the band gap energy value (GaN: 3.4 eV) of the compound semiconductor constituting the interface layer 72A of the second compound semiconductor layer 72. As a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor (specifically, GaN) constituting the interface layer 72A of the second compound semiconductor layer 72, specifically, the contact layer 74 includes:
_{_{(A) Al X Ga Y In}} Z N ( where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1) consisting of structure _{_{(b) Al X Ga Y In}} Z N S O _T (where X + Y + Z = 1, 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ Z ≦ 1, 0 <S ≦ 1, 0 <T ≦ 1) (c) Al _X Ga _Y In _Z N _{_S} P _{_1-S} (where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1,0 ≦ S <1) consisting of structure _{_{(d) Al X Ga Y In}} Z N _{_S} As _{_1-S} (where, X + Y + Z = 1,0 ≦ X ≦ 1,0 ≦ Y ≦ 1,0 ≦ Z ≦ 1,0 ≦ S <1) consists _{_{(e) Al X Ga Y In}} Z N S Sb _1-S (where X + Y + Z = 1, 0 ≦ X ≦ 1, 0 ≦ Y ≦ 1, 0 ≦ Z ≦ 1, 0 ≦ S <1) can be exemplified. In addition, the value of the band gap energy of these materials is all smaller than, for example, 3.3 eV and 3.4 eV.

Even in the contact layer 74 in the electronic device of Example 5 described above,
(Z _C '/ x _C ')> (z ₂ / x ₂ )
Was satisfied. In addition, the contact layer 74 is pseudo-lattice matched with the interface layer 72 A of the second compound semiconductor layer 72. That is, when the lattice constant along the x axis of the crystal constituting the contact layer 74 is x _C and the lattice constant along the z axis is z _C ,
x ₂ = x _C '<x _C
z _C '> z _C
Was satisfied. Further, when the contact layer 74 having a thickness of two atomic layers is provided between the interface layer 72A made of p-type GaN and the second electrode 92 made of ITO, a series estimated from the work function value of ITO. With respect to the resistance value, the series resistance value of the electronic device of Example 5 was reduced to about 2/3.

That is, as described above, even in the electronic device of Example 5, the lattice constant in the interface layer, which is the portion of the two-compound semiconductor layer in contact with the contact layer, and the length in one unit of the crystals constituting the contact layer are Since the predetermined relationship is satisfied, a kind of distortion occurs in the contact layer. As a result, not only can the drive voltage be reduced, but also a material having a low work function value such as ITO can be used. It becomes possible to constitute two electrodes, and the degree of freedom of selection of the material constituting the second electrode can be improved.

Example 6 is a modification of Example 1 and relates to an electronic device having the configuration 2-B. 11A and 11B are schematic partial cross-sectional views of the electronic device of Example 6. FIG. 11A and 11B are schematic partial sectional views similar to those taken along the arrow AA in FIG. 7B, and are virtual planes perpendicular to the extending direction of the waveguide structure (resonator structure). It is a typical partial sectional view when an electronic device is cut.

In the electronic device of Example 6,
The light emitting / receiving layer 20 is a stacked structure including a first compound semiconductor layer 71 having a first conductivity type, an active layer 73, and a second compound semiconductor layer 72 having a second conductivity type different from the first conductivity type. 70
A first electrode 91 is formed on the first compound semiconductor layer 71 via a contact layer 75,
The thickness of the contact layer 75 is a thickness of 4 atomic layers or less,
The interface between the contact layer 75 and the first compound semiconductor layer 71 is the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer 71A that is the portion of the first compound semiconductor layer 71 in contact with the contact layer 75 is x ₁ , When the lattice constant along the z-axis is z ₁ , the length along the x-axis in one unit of the crystal constituting the contact layer 75 is x _C ″, and the length along the z-axis is z _C ″
(Z _C ″ / x _C ″)> (z ₁ / x ₁ )
Satisfied.

The ridge stripe structure 60 has the same structure and configuration as the ridge stripe structure 60 in the electronic device of the fourth embodiment. Here, in Example 6, the second electrode 92 is made of the same material as the second electrode 32 of Example 1, and the first electrode 91 is made of ITO, Cu, Ti, Al, Ta, or the like.

The crystal structure of the crystal constituting the interface layer 71A of the first compound semiconductor layer 71 is a hexagonal system. The crystal structure of the crystals constituting the contact layer 75 is also hexagonal. The laminated structure 70 is made of a GaN-based compound semiconductor, and the contact layer 75 is a GaN-based compound semiconductor having the same composition as the GaN-based compound semiconductor constituting the interface layer 71A of the first compound semiconductor layer 71, and further oxygen It consists of a GaN-based compound semiconductor containing atoms. The composition of the laminated structure 70 is the same as that shown in Table 4 above. Alternatively, the laminated structure 70 is made of a GaN-based compound semiconductor, and the contact layer 75 is made of a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the interface layer 71A of the first compound semiconductor layer 71.

The electronic device of Example 6 is the same as the [Step-400] to [Step-410] except for the formation of the contact layer 74 in [Step-400] in the electronic device manufacturing method of Example 4. In the same step as [Step-420], the insulating layer 80 is formed on the entire surface, and the portion of the insulating layer 80 located on the top surface of the second compound semiconductor layer 72 is removed. Then, the second electrode 92 is formed on the exposed second compound semiconductor layer 72 (see FIG. 11A). Alternatively, the second electrode 92 is formed on the entire surface, and the portion of the second electrode 92 located on the top surface of the second compound semiconductor layer 72 is left. Then, after the insulating layer 80 is formed on the entire surface, a part of the insulating layer 80 may be removed to expose a part of the second electrode 92 (see FIG. 11B). Thereafter, a part of the insulating layer 80 on the first compound semiconductor layer 71 is removed, a part of the first compound semiconductor layer 71 is exposed, and on the exposed first compound semiconductor layer 71, a contact layer 75, By forming the first electrode 91, the structure shown in FIG. 11 can be obtained. Thereafter, the same step as [Step-430] in Embodiment 4 may be performed.

Even in the contact layer 75 in the electronic device of Example 6 described above,
(Z _C ″ / x _C ″)> (z ₁ / x ₁ )
Was satisfied. In addition, the contact layer 75 is pseudo-lattice matched with the interface layer 71 A of the first compound semiconductor layer 71. That is, when the lattice constant along the x axis of the crystal constituting the contact layer 75 is x _C and the lattice constant along the z axis is z _C ,
x ₁ = x _C ″ <x _C
z _C ”> z _C
Was satisfied. In addition, since the contact layer 75 having a thickness of two atomic layers was provided between the interface layer 71A and the first electrode 91, the series resistance value of the electronic device of Example 6 was a sufficiently small value.

That is, as described above, even in the electronic device of Example 6, the lattice constant in the interface layer, which is the portion of the first compound semiconductor layer in contact with the contact layer, and the length in one unit of the crystals constituting the contact layer are Since the predetermined relationship is satisfied, a kind of distortion occurs in the contact layer, and as a result, the contact resistance value can be further reduced.

Example 7 relates to a solid-state imaging device of the present disclosure. The solid-state imaging apparatus according to the seventh embodiment includes the electronic devices (specifically, photoelectric conversion elements) according to the first to third embodiments.

FIG. 12 shows a conceptual diagram of the solid-state imaging device (solid-state imaging device) of Example 7. The solid-state imaging device 100 according to the seventh embodiment includes an imaging region in which the electronic devices (photoelectric conversion elements) 10 described in the first to third embodiments are arranged in a two-dimensional array on a semiconductor substrate (for example, a silicon semiconductor substrate). 101, a vertical drive circuit 102 as a peripheral circuit thereof, a column signal processing circuit 103, a horizontal drive circuit 104, an output circuit 105, a control circuit 106, and the like. Note that these circuits can be configured from well-known circuits, and can be configured using other circuit configurations (for example, various circuits used in conventional CCD imaging devices and CMOS imaging devices). Needless to say, it can be done.

The control circuit 106 generates a clock signal and a control signal that serve as a reference for the operation of the vertical drive circuit 102, the column signal processing circuit 103, and the horizontal drive circuit 104 based on the vertical synchronization signal, the horizontal synchronization signal, and the master clock. The generated clock signal and control signal are input to the vertical drive circuit 102, the column signal processing circuit 103, and the horizontal drive circuit 104.

The vertical drive circuit 102 is configured by a shift register, for example, and selectively scans each electronic device 10 in the imaging region 101 in the vertical direction sequentially in units of rows. Then, a pixel signal based on a current (signal) generated according to the amount of received light in each electronic device 10 is sent to the column signal processing circuit 103 via the vertical signal line 107.

The column signal processing circuit 103 is arranged, for example, for each column of the electronic devices 10, and outputs a signal output from the electronic device 10 for one row for each electronic device 10 with a black reference pixel (not shown, but an effective pixel region). Signal processing for signal removal and signal amplification. At the output stage of the column signal processing circuit 103, a horizontal selection switch (not shown) is connected between the horizontal signal line 108 and provided.

The horizontal drive circuit 104 is configured by, for example, a shift register, and sequentially selects each of the column signal processing circuits 103 by sequentially outputting horizontal scanning pulses, and signals from each of the column signal processing circuits 103 are sent to the horizontal signal line 108. Output.

The output circuit 105 performs signal processing on the signals sequentially supplied from each of the column signal processing circuits 103 via the horizontal signal line 108 and outputs the signals.

Although depending on the material constituting the light emitting / receiving layer, since the light emitting / receiving layer itself can function as a color filter, color separation is possible without providing a color filter. However, in some cases, a known color filter that transmits a specific wavelength such as red, green, blue, cyan, magenta, yellow, or the like may be disposed above the light incident side of the electronic device 10. Good. Further, the solid-state imaging device can be a front-side irradiation type or a back-side irradiation type. Moreover, you may arrange | position the shutter for controlling incidence | injection of the light to the electronic device 10 as needed.

Although the present disclosure has been described based on the preferred embodiments, the present disclosure is not limited to these embodiments. The structure and configuration of the electronic device (photoelectric conversion element), the solid-state imaging device, and the semiconductor laser element described in the examples, the manufacturing conditions and manufacturing method of the electronic device, and the materials used are examples, and can be changed as appropriate. The electronic device described in Embodiments 4 to 5 and the electronic device described in Embodiment 6 can be combined. When the electronic device of the present disclosure is to function as a solar cell, the light emitting / receiving layer may be irradiated with light without applying a voltage between the first electrode and the second electrode. In addition to an imaging device (solid-state imaging device) such as a television camera, an optical sensor or an image sensor can be configured by the electronic device of the present disclosure. In addition to the semiconductor laser element, as an electronic device, a semiconductor light emitting element such as a super luminescent diode (SLD), a surface emitting laser element, a light emitting diode (LED), or a semiconductor optical amplifier can be used. It can also be a solar cell or a light sensor.

In the fourth to sixth embodiments, the ridge stripe structure 60 has a linearly extending shape, but the present invention is not limited to this. Or flare shape. Specifically, for example, a structure that is monotonously and gradually widened in a tapered manner from the light emitting end face toward the light reflecting end face, first widened from the light emitting end face toward the light reflecting end face, and exceeds the maximum width. After that, it can be configured to be narrowed.

Furthermore, the semiconductor laser element may be a semiconductor laser element having an oblique ridge stripe type separated confinement heterostructure having an oblique waveguide. In such a semiconductor laser element, for example, it has a structure in which two linear ridge stripe structures are combined, and the value of the angle φ at which the two ridge stripe structures intersect is, for example,
0 <φ ≦ 10 (degrees)
Preferably,
0 <φ ≦ 6 (degrees)
Is desirable. By adopting the oblique ridge stripe type, the reflectance of the light emitting end face coated with non-reflective coating can be made closer to the ideal value of 0%, and as a result, the laser light that circulates in the semiconductor laser element can be obtained. Generation | occurrence | production can be prevented and the advantage that generation | occurrence | production of the secondary induced emission light accompanying the main induced emission light can be suppressed can be acquired.

In addition, this indication can also take the following structures.
[A01] << Electronic device >>
A light emitting / receiving layer, a first electrode electrically connected to the light emitting / receiving layer, and a second electrode formed on the light emitting / receiving layer,
The second electrode is composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen,
The light emitting / receiving layer is covered with an insulating layer composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen,
An electronic device in which the composition ratio of oxygen in the insulating layer is higher than the composition ratio of oxygen in the second electrode.
[A02] The second electrode is made of In _a (Ga, Al) _b Zn _c O _d ,
The electronic device according to [A01], wherein the insulating layer is made of In _a (Ga, Al) _b Zn _c O _e (where d <e).
[A03] The insulating layer and the second electrode are made of indium-gallium oxide, indium-doped gallium-zinc oxide, aluminum oxide-doped zinc oxide, indium-zinc oxide, or gallium-doped zinc oxide. The electronic device according to [A01] or [A02] configured.
[A04] The electronic device according to any one of [A01] to [A03], wherein the internal stress of the insulating layer is a compressive stress of 10 MPa to 90 MPa.
[A05] The electronic device according to any one of [A01] to [A04], wherein the light transmittance of the insulating layer with respect to light having a wavelength of 400 nm to 660 nm is 80% or more.
[A06] The electronic device according to any one of [A01] to [A05], wherein the light transmittance of the second electrode with respect to light having a wavelength of 400 nm to 660 nm is 75% or more.
[A07] The electronic device according to any one of [A01] to [A06], in which a sheet resistance value of the second electrode is 3 × 10Ω / □ to 1 × 10 ³ Ω / □.
[A08] The composition ratio of oxygen in the second electrode and the insulating layer is controlled by controlling the oxygen gas partial pressure when forming the second electrode and the insulating layer based on the sputtering method. [A01] to [A07] The electronic device according to any one of the above.
[A09] << Configuration 1-A >>
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The electronic device according to any one of [A01] to [A08], wherein a difference between a work function value of the second electrode and a work function value of the first electrode is 0.4 eV or more.
[B01] By setting the difference between the work function value of the second electrode and the work function value of the first electrode to 0.4 eV or more, an internal electric field is generated in the light emitting / receiving layer based on the difference of the work function values. The electronic device according to [A09], which improves internal quantum efficiency.
[A10] << Configuration 1-B >>
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The second electrode has a laminated structure of the second B layer and the second A layer from the light emitting / receiving layer side,
The electronic device according to any one of [A01] to [A08], in which a work function value of the second A layer of the second electrode is lower than a work function value of the second B layer of the second electrode.
[B02] The electronic device according to [A10], wherein a difference between a work function value of the second A layer of the second electrode and a work function value of the second B layer of the second electrode is 0.1 eV to 0.2 eV. .
[B03] The electronic device according to [A10] or [B02], in which a difference between a work function value of the first electrode and a work function value of the second A layer of the second electrode is 0.4 eV or more.
[B04] The thickness of the second electrode is 1 × 10 ⁻⁸ m to 1 × 10 ⁻⁷ m,
The electronic device according to any one of [A10] to [B03], wherein the ratio of the thickness of the second A layer of the second electrode to the thickness of the second B layer of the second electrode is 9/1 to 1/9.
[B05] By setting the difference between the work function value of the first electrode and the work function value of the second A layer of the second electrode to 0.4 eV or more, in the light emitting / receiving layer based on the difference of the work function values The electronic device according to any one of [A10] to [B04], which generates an internal electric field to improve internal quantum efficiency.
[B06] The electronic device according to any one of [A09] to [B05], in which a work function value of the second electrode is 4.1 eV to 4.5 eV.
[B07] The electronic device according to any one of [A09] to [B06], wherein the first electrode is made of indium-tin oxide, indium-zinc oxide, or tin oxide.
[B08] The work function value of the second electrode is controlled by controlling the amount of oxygen gas introduced when the second electrode is formed based on the sputtering method. Any one of [A09] to [B07] The electronic device described.
[B09] The electronic device according to any one of [A09] to [B08], wherein the oxygen content is lower than the oxygen content of the stoichiometric composition.
[A11] The electronic device according to any one of [A01] to [B09], wherein the light emitting / receiving layer is made of an organic photoelectric conversion material.
[A12] The electronic device according to [A11], including a photoelectric conversion element.
[A13] << Configuration 2-A >>
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A second electrode is formed on the second compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the second compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the second compound semiconductor layer in contact with the contact layer is along the x ₂ and z axes. When the lattice constant is z ₂ , the length along the x-axis in one unit of the crystal constituting the contact layer is x _C ′, and the length along the z-axis is z _C ′,
(Z _C '/ x _C ')> (z ₂ / x ₂ )
[A01] to [A08] according to any one of [A01] to [A08].
[C01] The electronic device according to [A13], wherein the contact layer is pseudo-lattice matched with the interface layer of the second compound semiconductor layer.
[C02] When the lattice constant along the x-axis of the crystal constituting the contact layer is x _C and the lattice constant along the z-axis is z _C ,
x ₂ = x _C '<x _C
z _C '> z _C
The electronic device according to [C01], wherein:
[C03] The crystal structure of the crystal constituting the interface layer of the second compound semiconductor layer is a hexagonal system,
The electronic device according to any one of [A13] to [C02], in which a crystal structure of a crystal forming the contact layer is a hexagonal system.
[C04] The laminated structure is made of a GaN-based compound semiconductor,
The electronic device according to [C03], wherein the contact layer is a GaN-based compound semiconductor having the same composition as that of the GaN-based compound semiconductor constituting the second compound semiconductor layer, and further includes a GaN-based compound semiconductor containing oxygen atoms.
[C05] The laminated structure is made of a GaN-based compound semiconductor,
The electronic device according to [C03], wherein the contact layer is made of a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the second compound semiconductor layer.
[C06] The laminated structure is composed of a GaN-based compound semiconductor,
The electronic device according to any one of [A13] to [C02], wherein the contact layer is made of one material selected from the group consisting of ZnO, ZnSe, CdO, CdS, and CdSe.
[C07] The band gap energy value of the compound semiconductor constituting the contact layer is any of [A13] to [C06] smaller than the band gap energy value of the compound semiconductor constituting the interface layer of the second compound semiconductor layer. The electronic device according to Item 1.
[C08] The electronic device according to any one of [A13] to [C07], in which the first conductivity type is n-type and the second conductivity type is p-type.
[D01]
A first electrode is formed on the first compound semiconductor layer via a second contact layer,
The thickness of the second contact layer is a thickness of 4 atomic layers or less,
The interface between the second contact layer and the first compound semiconductor layer is the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the first compound semiconductor layer in contact with the second contact layer is x _1. , The lattice constant along the z-axis is z ₁ , the length along the x-axis in one unit of the crystal constituting the second contact layer is x _C ″, and the length along the z-axis is z _C ″. When
(Z _C ″ / x _C ″)> (z ₁ / x ₁ )
The electronic device according to any one of [A13] to [C08] that satisfies the above.
[D02] The electronic device according to [D01], in which the second contact layer is pseudo-lattice matched with the interface layer of the first compound semiconductor layer.
[D03] When the lattice constant along the x-axis of the crystal constituting the second contact layer is x _C and the lattice constant along the z-axis is z _C ,
x ₁ = x _C ″ <x _C
z _C ”> z _C
The electronic device according to [D02], which satisfies:
[D04] The crystal structure of the crystal constituting the interface layer of the first compound semiconductor layer is a hexagonal system,
The electronic device according to any one of [D01] to [D03], in which a crystal structure of a crystal forming the second contact layer is a hexagonal system.
[D05] The second contact layer is a GaN-based compound semiconductor having the same composition as that of the GaN-based compound semiconductor constituting the first compound semiconductor layer, and further includes a GaN-based compound semiconductor containing oxygen atoms. The electronic device described.
[D06] The electronic device according to [D04], in which the second contact layer is formed of a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the first compound semiconductor layer.
[D07] The electronic device according to any one of [D01] to [D03], in which the second contact layer is made of one material selected from the group consisting of ZnO, ZnSe, CdO, CdS, and CdSe.
[D08] The value of the band gap energy of the compound semiconductor constituting the second contact layer is smaller than the value of the band gap energy of the compound semiconductor constituting the interface layer of the first compound semiconductor layer [D01] to [D07]. The electronic device according to any one of the above.
[A14] << Configuration 2-B >>
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A first electrode is formed on the first compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the first compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the first compound semiconductor layer in contact with the contact layer is along the x ₁ and z axes. When the lattice constant is z ₁ , the length along the x-axis in one unit of the crystal constituting the contact layer is x _C ″, and the length along the z-axis is z _C ″
(Z _C ″ / x _C ″)> (z ₁ / x ₁ )
[A01] to [A08] according to any one of [A01] to [A08].
[E01] The electronic device according to [A14], wherein the contact layer is pseudo-lattice matched with the interface layer of the first compound semiconductor layer.
[E02] When the lattice constant along the x-axis of the crystal constituting the contact layer is x _C and the lattice constant along the z-axis is z _C ,
x ₁ = x _C ″ <x _C
z _C ”> z _C
The electronic device according to [E01], wherein:
[E03] The crystal structure of the crystal constituting the interface layer of the first compound semiconductor layer is a hexagonal system,
The electronic device according to any one of [A14] to [E02], wherein a crystal structure of a crystal forming the contact layer is a hexagonal system.
[E04] The laminated structure is made of a GaN-based compound semiconductor,
The electronic device according to [E03], wherein the contact layer is a GaN-based compound semiconductor having the same composition as the GaN-based compound semiconductor constituting the first compound semiconductor layer, and further includes a GaN-based compound semiconductor containing oxygen atoms.
[E05] The laminated structure is made of a GaN-based compound semiconductor,
The electronic device according to [E03], wherein the contact layer is made of a GaN-based compound semiconductor having a composition different from that of the GaN-based compound semiconductor constituting the first compound semiconductor layer.
[E06] The laminated structure is composed of a GaN-based compound semiconductor,
The electronic device according to any one of [A14] to [E02], wherein the contact layer is made of one material selected from the group consisting of ZnO, ZnSe, CdO, CdS, and CdSe.
[E07] The band gap energy value of the compound semiconductor constituting the contact layer is any of [A14] to [E06] smaller than the band gap energy value of the compound semiconductor constituting the interface layer of the first compound semiconductor layer. The electronic device according to Item 1.
[E08] The electronic device according to any one of [A14] to [E07], wherein the first conductivity type is an n-type and the second conductivity type is a p-type.
[F01] << Solid-state imaging device >>
A solid-state imaging device comprising the electronic device according to any one of [A01] to [A12].
[G01] << Method for Manufacturing Electronic Device >>
A second electrode composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen is formed on the light emitting / receiving layer based on a sputtering method;
The light emitting / receiving layer is covered with an insulating layer composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen based on a sputtering method.
Including at least a step,
A method for manufacturing an electronic device, wherein the oxygen composition ratio in the insulating layer is made higher than the oxygen composition ratio in the second electrode by controlling the oxygen gas partial pressure when forming the second electrode and the insulating layer based on the sputtering method. .
[G02] The method for manufacturing an electronic device according to [G01], in which an oxygen gas partial pressure when forming the insulating layer based on a sputtering method is set to 0.04 Pa to 0.15 Pa.
[G03] The method for manufacturing an electronic device according to [G01] or [G02], wherein a temperature at which the insulating layer is formed based on a sputtering method is set to 25 ° C. to 28 ° C.
[G04] The electronic device manufacturing method according to any one of [G01] to [G03], in which the electronic device constitutes a photoelectric conversion element.
[H01] The difference between the work function value of the second electrode and the work function value of the first electrode is 0.4 eV or more,
The method for manufacturing an electronic device according to any one of [G01] to [G04], wherein the work function value of the second electrode is controlled by controlling the amount of oxygen gas introduced when forming based on a sputtering method.
[H02] By setting the difference between the work function value of the second electrode and the work function value of the first electrode to 0.4 eV or more, an internal electric field is generated in the light emitting / receiving layer based on the difference of the work function values. The method for manufacturing an electronic device according to [H01], which improves internal quantum efficiency.
[H03] The second electrode has a laminated structure of the second B layer and the second A layer from the light emitting / receiving layer side,
The work function value of layer 2A of the second electrode is lower than the work function value of layer 2B of the second electrode,
By controlling the amount of oxygen gas introduced when forming based on the sputtering method, the work function values of the second A layer and the second B layer of the second electrode are controlled. Any one of [G01] to [G04] The manufacturing method of the electronic device of description.
[H04] The electronic device according to [H03], wherein the difference between the work function value of the second electrode 2A layer and the work function value of the second electrode layer 2B is 0.1 eV to 0.2 eV. Manufacturing method.
[H05] The thickness of the second electrode is 1 × 10 ⁻⁸ m to 1 × 10 ⁻⁷ m,
The method of manufacturing an electronic device according to [H03] or [H04], wherein the ratio of the thickness of the second electrode 2A layer to the thickness of the second electrode layer 2B is 9/1 to 1/9.
[H06] By setting the difference between the work function value of the first electrode and the work function value of the second electrode 2A layer to 0.4 eV or more, in the light emitting / receiving layer based on the work function value difference. The method for manufacturing an electronic device according to any one of [H03] to [H05], wherein an internal electric field is generated to improve internal quantum efficiency.
[H07] The method for manufacturing an electronic device according to any one of [H01] to [H06], wherein the oxygen content in the second electrode is smaller than the oxygen content in the stoichiometric composition.
[H08] The method of manufacturing an electronic device according to any one of [H01] to [H07], in which a work function value of the second electrode is 4.1 eV to 4.5 eV.
[H09] The method for manufacturing an electronic device according to any one of [H01] to [H08], wherein the first electrode is made of indium-tin oxide, indium-zinc oxide, or tin oxide.
[J01] << Insulating material >>
An insulating material composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen.
[J02] The insulating material according to [J01], which is made of In _a (Ga, Al) _b Zn _c O _e .
[J03] [J01] or [J02] composed of indium-gallium oxide, indium-doped gallium-zinc oxide, aluminum oxide-doped zinc oxide, indium-zinc oxide, or gallium-doped zinc oxide Insulating material described in 1.
[J04] The insulating material according to any one of [J01] to [J03], wherein the internal stress of the insulating layer obtained by forming the insulating material is a compressive stress of 10 MPa to 90 MPa.
[J05] The insulating material according to any one of [J01] to [J04], which has a light transmittance of 80% or more for light having a wavelength of 400 nm to 660 nm.

DESCRIPTION OF SYMBOLS 10 ... Electronic device, 11 ... Board | substrate, 12 ... Wiring, 13 ... Interlayer insulation film, 14 ... Opening part, 20 ... Light emitting / light-receiving layer, 31 and 91 ... 1st 1 electrode, 32, 92 ... 2nd electrode, 32A ... 2nd A layer of 2nd electrode, 32B ... 2nd B layer of 2nd electrode, 40, 80 ... insulating layer, 51 ... GaN substrate, 52 ... buffer layer, 60 ... ridge stripe structure, 61 ... light emitting end face (first end face), 62 ... light reflecting end face (second end face), 70 ... laminated structure 71, the first compound semiconductor layer, 71 A, the interface layer of the first compound semiconductor layer, 72, the second compound semiconductor layer, 72 A, the interface layer of the second compound semiconductor layer, 73. ..Active layer, 74, 75... Contact layer, 100... Solid imaging device, 101. ... Vertical drive circuit, 103 ... Column signal processing circuit, 104 ... Horizontal drive circuit, 105 ... Output circuit, 106 ... Control circuit, 107 ... Vertical signal line, 108 ... Horizontal signal line

Claims

A light emitting / receiving layer, a first electrode electrically connected to the light emitting / receiving layer, and a second electrode formed on the light emitting / receiving layer,
The second electrode is composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen,
The light emitting / receiving layer is covered with an insulating layer composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen,
An electronic device in which the composition ratio of oxygen in the insulating layer is higher than the composition ratio of oxygen in the second electrode.
The second electrode is made of In a (Ga, Al) b Zn c O d ,
The electronic device according to claim 1, wherein the insulating layer is made of In a (Ga, Al) b Zn c O e (where d <e).
The insulating layer and the second electrode are composed of indium-gallium oxide, indium-doped gallium-zinc oxide, aluminum oxide-doped zinc oxide, indium-zinc oxide, or gallium-doped zinc oxide. The electronic device according to claim 1.
2. The electronic device according to claim 1, wherein the internal stress of the insulating layer is a compressive stress of 10 MPa to 90 MPa.
The electronic device according to claim 1, wherein the light transmittance of the insulating layer with respect to light having a wavelength of 400 nm to 660 nm is 80% or more.
The electronic device according to claim 1, wherein the light transmittance of the second electrode with respect to light having a wavelength of 400 nm to 660 nm is 75% or more.
The electronic device according to claim 1, wherein the sheet resistance value of the second electrode is 3 × 10 Ω / □ to 1 × 10 3 Ω / □.
2. The electronic device according to claim 1, wherein the composition ratio of oxygen in the second electrode and the insulating layer is controlled by controlling an oxygen gas partial pressure when forming the second electrode and the insulating layer based on a sputtering method.
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The electronic device according to claim 1, wherein a difference between a work function value of the second electrode and a work function value of the first electrode is 0.4 eV or more.
The light emitting / receiving layer is sandwiched between the first electrode and the second electrode,
The second electrode has a laminated structure of the second B layer and the second A layer from the light emitting / receiving layer side,
2. The electronic device according to claim 1, wherein the work function value of the second A layer of the second electrode is lower than the work function value of the second B layer of the second electrode.
The electronic device according to claim 1, wherein the light emitting / receiving layer is made of an organic photoelectric conversion material.
The electronic device according to claim 11, comprising a photoelectric conversion element.
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A second electrode is formed on the second compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the second compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the second compound semiconductor layer in contact with the contact layer is along the x 2 and z axes. When the lattice constant is z 2 , the length along the x-axis in one unit of the crystal constituting the contact layer is x C ′, and the length along the z-axis is z C ′,
(Z C '/ x C ')> (z 2 / x 2 )
The electronic device according to claim 1, wherein:
The light emitting / receiving layer is composed of a laminated structure including a first compound semiconductor layer having a first conductivity type, an active layer, and a second compound semiconductor layer having a second conductivity type different from the first conductivity type,
A first electrode is formed on the first compound semiconductor layer via a contact layer,
The thickness of the contact layer is a thickness of 4 atomic layers or less,
The interface between the contact layer and the first compound semiconductor layer is along the xy plane, and the lattice constant along the x axis of the crystal constituting the interface layer that is the portion of the first compound semiconductor layer in contact with the contact layer is along the x 1 and z axes. When the lattice constant is z 1 , the length along the x-axis in one unit of the crystal constituting the contact layer is x C ″, and the length along the z-axis is z C ″
(Z C ″ / x C ″)> (z 1 / x 1 )
The electronic device according to claim 1, wherein:
A solid-state imaging device comprising the electronic device according to any one of claims 1 to 12.
A second electrode composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen is formed on the light emitting / receiving layer based on a sputtering method;
The light emitting / receiving layer is covered with an insulating layer composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen based on a sputtering method.
Including at least a step,
A method for manufacturing an electronic device, wherein the oxygen composition ratio in the insulating layer is made higher than the oxygen composition ratio in the second electrode by controlling the oxygen gas partial pressure when forming the second electrode and the insulating layer based on the sputtering method. .
The method for manufacturing an electronic device according to claim 16, wherein an oxygen gas partial pressure when forming the insulating layer based on a sputtering method is 0.04 Pa to 0.15 Pa.
The method for manufacturing an electronic device according to claim 16, wherein a temperature at which the insulating layer is formed based on a sputtering method is set to 22 ° C to 28 ° C.
The electronic device manufacturing method according to claim 16, wherein the electronic device constitutes a photoelectric conversion element.
An insulating material composed of at least a quaternary compound of indium, gallium and / or aluminum, zinc, and oxygen.