WO2012137795A1 - 受光素子およびその製造方法 - Google Patents
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- WO2012137795A1 WO2012137795A1 PCT/JP2012/059137 JP2012059137W WO2012137795A1 WO 2012137795 A1 WO2012137795 A1 WO 2012137795A1 JP 2012059137 W JP2012059137 W JP 2012059137W WO 2012137795 A1 WO2012137795 A1 WO 2012137795A1
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- semiconductor layer
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- light receiving
- receiving element
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035236—Superlattices; Multiple quantum well structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
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- H01L21/02507—Alternating layers, e.g. superlattice
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Definitions
- the present invention relates to a light receiving element and a method for manufacturing the same. More specifically, in the type 2 multiple quantum well structure (Multi-QuantumMWell, hereinafter referred to as MQW) having light receiving sensitivity in the near-infrared region, the wavelength can be further increased without increasing the dark current.
- MQW multiple quantum well structure
- the present invention relates to a light receiving element capable of expanding the light receiving sensitivity and a manufacturing method thereof.
- Non-Patent Document 1 proposes a photodiode having a cut-off wavelength of 2.39 ⁇ m by forming an InGaAs / GaAsSb type 2 MQW on an InP substrate and a pn junction formed by a p-type or n-type epitaxial layer. Sensitivity characteristics with wavelengths of 1.7 ⁇ m to 2.7 ⁇ m are shown.
- Non-Patent Document 2 shows the sensitivity characteristic (200K, 250K, 295K) of a wavelength of 1 ⁇ m to 3 ⁇ m of a light receiving element having a type 2 MQW light receiving layer in which 150 pairs of InGaAs 5 nm and GaAsSb 5 nm are stacked as a pair. .
- the present invention has an object to provide a light receiving element and a method for manufacturing the same, which can expand the light receiving sensitivity to the long wavelength side of the near infrared without increasing the dark current.
- the light receiving element of the present invention is a light receiving element made of a III-V group compound semiconductor.
- the light receiving element is provided on a group III-V compound semiconductor substrate, and includes a light receiving layer of a type 2 multiple quantum well structure in which first semiconductor layers and second semiconductor layers are alternately stacked, In one semiconductor layer, a composition gradient is provided in the thickness direction so that the band gap energy of the first semiconductor layer decreases toward the upper surface or the lower surface.
- the band gap energy becomes the smallest at the end face (upper surface or lower surface) of the layer having a composition gradient in which the band gap energy becomes small. That is, the valence band takes the highest energy position and the conduction band takes the lowest energy position. Therefore, regardless of whether the first semiconductor layer is a layer with a higher valence band or a layer with a lower valence band in a type 2 multiple quantum well structure, the transition width in the type 2 transition (Energy difference in type 2 transition) becomes smaller. (1) When the first semiconductor layer is a layer having a higher valence band, when light is received, electrons in the valence band of the first semiconductor layer are transmitted in the conduction band of the second semiconductor layer.
- the dark current is as follows.
- the band gap energy is the largest at the end surface opposite to the end surface where the band gap energy is the smallest in the first semiconductor layer.
- the band gap energy corresponding to the average composition of the first semiconductor layer is the average band gap energy in the first semiconductor layer. Since the dark current is determined by this average band gap energy, for example, the band gap energy at one end face is minimized while maintaining the dark current at a constant reference with the average composition of the first semiconductor layer as a reference. Thus, the wavelength can be increased.
- the first and second layers in the first semiconductor layer and the second semiconductor layer are not related to the order of stacking. For example, “first” may be replaced with “one” and “second” may be replaced with “the other”. Further, the first semiconductor layer may be a layer having a higher or lower valence band in a band structure of a type 2 multiple quantum well structure.
- the band gap energy of the second semiconductor layer is reduced to a surface in contact with the end face which is given a gradient so that the band gap energy is reduced in the first semiconductor layer.
- the composition can have a gradient in the thickness direction.
- the energy difference lower limit interface In the first and second semiconductor layers, on the surface opposite to the lower limit interface, the band gap energy is maximized in both layers because of the composition gradient. This interface is called the energy difference upper limit interface.
- the energy difference lower limit interface and the energy difference upper limit interface are alternately positioned in the thickness direction.
- the composition at the end face at the extreme position where the band gap energy is reduced is the value of each semiconductor layer.
- the degree of lattice mismatch exceeds 0.2% in terms of change in lattice constant.
- the average composition of at least one of the first semiconductor layer and the second semiconductor layer is converted into a change in lattice constant, and the degree of lattice mismatch with the III-V compound semiconductor substrate is ⁇ 1. % Should be within.
- the average lattice mismatch with respect to the III-V compound semiconductor substrate of each semiconductor layer can be limited within a certain range, and misfit dislocations are prevented from occurring while a composition gradient is provided in the thickness direction. Can do.
- the semiconductor layer having the higher valence band potential energy may include at least one of Ga, As, and Sb.
- a III-V group compound semiconductor such as GaAsSb can be used for the semiconductor layer having a higher valence band.
- the semiconductor layer with the lower potential energy in the valence band may include at least one of In, Ga, and As.
- a III-V group compound semiconductor such as InGaAs can be used for the semiconductor layer having a lower valence band.
- the average composition y ave of GaAs 1-y Sb y layer (0. 36 ⁇ y ave ⁇ 0.62) is preferable.
- the average lattice mismatch with respect to the substrate of the InGaAs layer and the GaAsSb layer can be kept within a certain range, and misfit dislocations are introduced.
- the above composition gradient can be easily applied in the thickness direction.
- the average composition x ave in the In x Ga 1-x As layer (0.38 ⁇ x ave ⁇ 0.68) is “in the compound semiconductor layer having the chemical formula of In x Ga 1-x As” x therein is equipped with a gradient in the thickness direction in the compound semiconductor layer, of course, the average value x ave over the thickness direction is present, the range of the average value x ave is, 0.38 ⁇ x ave ⁇ 0.68 ”.
- the y ave of GaAs 1-y Sb y layer is the same applies.
- the III-V compound semiconductor substrate is preferably an InP substrate. This makes it possible to efficiently mass-produce light receiving elements using a large-diameter InP substrate that is easily available.
- a light receiving element using a III-V compound semiconductor is manufactured.
- the manufacturing method includes a step of forming a light-receiving layer of a type 2 multiple quantum well structure by alternately laminating a first semiconductor layer and a second semiconductor layer on an InP substrate, and the multiple quantum well
- a composition gradient is given in the thickness direction so that the band gap energy of the first semiconductor layer is reduced toward the upper surface or the lower surface in the layer of the first semiconductor layer. .
- the band of the second semiconductor layer is formed in the second semiconductor layer toward a surface in contact with the end of the first semiconductor layer that is inclined so as to reduce the band gap. It is preferable to provide a composition gradient in the thickness direction so that the gap energy is reduced. Thereby, the energy difference lower limit interface can be easily formed, and the energy difference in the type 2 transition can be further reduced. In that case, naturally, the energy difference upper limit interface is also formed alternately. For this reason, since the average composition does not change and the substantial band gap energy does not change, the dark current can be kept low.
- the all-organic metal vapor deposition method When a multiple quantum well structure is formed by an all-organic metal vapor deposition method and a composition gradient is given to the first semiconductor layer or the first semiconductor layer and the second semiconductor layer, the all-organic metal vapor deposition method is used.
- the composition gradient may be adjusted by adjusting a mass flow controller (MFC) incorporated in the growth mechanism.
- MFC mass flow controller
- the all-organic metal vapor phase growth method refers to a growth method in which an organic metal raw material composed of a compound of an organic substance and a metal is used for all the raw materials for vapor phase growth, and is referred to as a total organic MOVPE method.
- the supply amount of each component of the first and second semiconductor layers is adjusted by a mass flow controller to change the composition as intended. Since the adjustment of the supply amount by the mass flow controller is highly accurate and accurate, the above-mentioned gradient can be given stably and with high reproducibility.
- the light receiving element or the like of the present invention it is possible to expand the light receiving sensitivity to the long wavelength side of the near infrared while keeping the dark current low.
- the light receiving layer 3 has a multiple quantum well structure formed by stacking InGaAs3a / GaAsSb3b having 50 to 300 quantum wells. At the interfaces 16 and 17 of the light receiving element 10, the oxygen and carbon concentrations are both less than 1 ⁇ 10 17 cm ⁇ 3 .
- Is a diagram for explaining the In x Ga 1-x As layer and the GaAs 1-y Sb y in the composition of the layer gradient (slope) constituting the MQW, left half semiconductor layer of FIG., The right half of FIG. It is a figure which shows distribution of the composition in a semiconductor layer.
- 1 InP substrate 2 buffer layer (InP and / or InGaAs), 3 type 2 MQW light receiving layer, 3a InGaAs layer, 3b GaAsSb layer, 4 InGaAs layer (diffusion concentration distribution adjusting layer), 5 InP window layer, 6 p-type region, 10 light receiving element, 11 p-side electrode (pixel electrode), 12 ground electrode (n-side electrode), 16 interface between MQW and InGaAs layer, 17 interface between InGaAs layer and InP window layer, 35 AR (antireflection) film, 36 selective diffusion mask pattern, 50a wafer (intermediate product), 60 all metal organic vapor phase deposition apparatus, 61 infrared temperature monitoring apparatus, 63 reaction chamber, 65 quartz tube, 69 reaction chamber window, 66 substrate table, 66h Heater, K Energy difference lower limit (minimum) interface, L Energy difference upper limit (maximum) interface.
- FIG. 1 is a diagram showing a light receiving element 10 according to an embodiment of the present invention.
- the light receiving element 10 has an InP-based semiconductor multilayer structure (epitaxial wafer) having the following configuration on the InP substrate 1.
- InP substrate side InP substrate side
- MQW Multi Quantum Well
- the p-type region 6 extending in the depth direction from the InP window layer 5 is formed by selectively diffusing Zn of the p-type impurity from the opening of the selective diffusion mask pattern 36 of the SiN film.
- a form in which diffusion is introduced into the periphery of the light receiving element 10 in a limited manner in a planar manner can be achieved by selective diffusion using the selective diffusion mask pattern 36 of the SiN film.
- a p-side electrode 11 made of AuZn is provided in the p-type region 6, and an n-side electrode 12 made of AuGeNi is provided in ohmic contact with the back surface of the InP substrate 1.
- the InP substrate 1 is doped with n-type impurities to ensure a predetermined level of conductivity.
- An SiON antireflection film 35 is also provided on the back surface of the InP substrate 1 so that light enters from the back surface side of the InP substrate.
- a pn junction is formed at the boundary front of the p-type region 6, and an n-type impurity is applied by applying a reverse bias voltage between the p-side electrode 11 and the n-side electrode 12.
- a depletion layer is generated more widely on the low concentration side (n-type impurity background).
- the background of the MQW light-receiving layer 3 is about 5 ⁇ 10 15 cm ⁇ 3 or less in terms of n-type impurity concentration (carrier concentration).
- the position of the pn junction is determined by the intersection of the background (n-type carrier concentration) of the light-receiving layer 3 of the multiple quantum well and the concentration profile of the p-type impurity Zn.
- the diffusion concentration distribution adjustment layer 4 is arranged for adjusting the concentration distribution of the p-type impurity in the MQW constituting the light receiving layer 3, but the diffusion concentration distribution adjustment layer 4 may be omitted.
- the Zn concentration is preferably 5 ⁇ 10 16 cm ⁇ 3 or less.
- Figure 2 is a diagram for explaining a gradient of composition of In x Ga 1-x As layer 3a and GaAs 1-y Sb y layer 3b constituting the MQW Type 2 in the light-receiving layer 3 (inclination).
- the left half of FIG. 2 shows the semiconductor layers 3a and 3b, and the right half of FIG. 2 shows the distribution of the compositions x and y in the semiconductor layers 3a and 3b.
- the composition x of the In x Ga 1-x As layer 3a is 0.53 at the thickness center as shown in FIG. 2, and the average composition x ave is 0.53, which is lattice-matched with InP. However, it rises to near 0.63 at the interface K.
- the composition x increases from around 0.43 at the interface L to around 0.63 at the interface K.
- the composition y increases from 0.43 at the interface L to around 0.54 at the interface K.
- the compositions x and y are drawn so as to change linearly in the thickness direction, and the composition at the center of the thickness is equal to the average composition, but the linearity of the composition gradient is not essential, and the step The gradient of the composition may be recognized macroscopically while wavy or accompanied by ripples. Therefore, the composition at the center of the thickness and the average composition do not necessarily match.
- FIG. 3 shows the MQW band structure with the gradient of composition x, y shown in FIG.
- the In x Ga 1-x As layer 3a has an In composition x that decreases in the growth direction (thickness direction toward the upper surface).
- GaAs 1-y Sb y layer 3b Sb composition y in the growth direction in is increased contrast.
- Such a composition gradient forms interfaces K and L as shown in FIGS.
- the composition x of In x Ga 1-x As layer 3a may also be a composition y of GaAs 1-y Sb y layer 3b, a maximum value.
- the band gap energy of the semiconductor layers on both sides decreases toward the interface K as shown in FIG.
- transition of the type 2 electrons in the valence band of the GaAs 1-y Sb y layer 3b whichever is higher valence band, absorbs the energy of light into the conduction band of the In x Ga 1-x As layer 3a To do.
- holes in the valence band of the GaAs 1-y Sb y layer 3b is also electrons in the conduction band of the In x Ga 1-x As layer 3a generates in pairs (Generation of hole-electron pairs).
- the valence band of the GaAs 1-y Sb y layer 3b at the interface K is the energy difference is minimum energy ⁇ Emin between the conduction band of the In x Ga 1-x As layer 3a, the wavelength of the corresponding light on the long wavelength
- the limit is ⁇ max.
- the above interface K can be referred to as an energy difference lower limit interface.
- the interface L can be called an energy difference upper limit interface.
- the band gap energy becomes the smallest at the end face (upper surface or lower surface) of the layer having a composition gradient in which the band gap energy becomes small in the semiconductor layer. That is, at the end face, the valence band takes the highest energy position and the conduction band takes the lowest energy position in the semiconductor layer. Therefore, in the In x Ga 1-x As layer 3a and GaAs 1-y Sb y layer 3b interface K both end faces band gap energy is small is in contact of the valence band and the conduction band are closest.
- the valence band of the GaAs 1-y Sb y layer 3b so at a higher energy position than the valence band of the In x Ga 1-x As layer 3a, when receiving light of the long wavelength of the upper limit, GaAs 1- y Sb y layer 3b of the valence band of electrons holes in the valence band of the in x Ga 1-x as layer 3a GaAs 1-y to the conduction band by the transition of type 2 Sb y layer 3b is Arise.
- the minimum energy difference ⁇ Emin at this time is shown in FIG.
- the probability that a hole exists at the position where the valence band is the highest is on the potential of the band (the potential is upside down with respect to the hole), and the GaAs 1-y Sb large in the layer of the y layer 3b, and an in x Ga probability of electrons located on the lowest position in the conduction band of 1-x As layer 3a, the potential, the layer in the in x Ga 1-x As layer 3a So big. For this reason, the probability that a hole / electron pair is generated by light reception increases. In other words, the light receiving efficiency of this type 2 is high.
- FIG. 3 shows a valence band and a conduction band corresponding to the average composition of the semiconductor layers 3a and 3b by broken lines. This broken line can be regarded as the valence band or conduction band of the band structure in the case of a composition lattice-matched to InP. According to FIG.
- the band gap energy becomes the largest at the end face opposite to the end face where the band gap energy is the smallest in each semiconductor layer (that is, the interface L). As described above, the band gap energy is the smallest at the interface K.
- the band gap corresponding to the average composition of the semiconductor layer is the average band gap energy in the semiconductor layer.
- the dark current is determined according to this average band gap energy. Therefore, it is possible to realize a longer wavelength by minimizing the band gap at one end face (energy difference lower limit interface K) while maintaining the dark current at a constant reference with the average composition of the semiconductor layer as a reference.
- FIG. 4 is a diagram showing a modified example of the band structure (FIG. 3) in the light receiving layer according to the first embodiment of the present invention.
- the light receiving element having the light receiving layer 3 of the modification shown in FIG. 4 is also a light receiving element of the present invention.
- the In x Ga 1-x As layer 3a has a graded composition in which the composition y increases toward the interface K only in the GaAs 1-y Sb y layer 3b. There is no gradient composition.
- FIG. 3 shows a graded composition in which the composition y increases toward the interface K only in the GaAs 1-y Sb y layer 3b. There is no gradient composition.
- FIG. 3 shows a graded composition in which the composition y increases toward the interface K only in the GaAs 1-y Sb y
- the valence band of the GaAs 1-y Sb y layer 3b is increased, since the conduction band of the In x Ga 1-x As layer 3a is flat, the energy difference ⁇ Emin is 3 Not as small as shown in However, compared to the case where both the layers 3a and 3b do not have a gradient composition, the energy difference in the type 2 transition can be surely reduced, which contributes to a longer wavelength in the light receiving region.
- FIG. 5 shows a piping system and the like of the film forming apparatus 60 of the all-organic metal vapor phase epitaxy method.
- a quartz tube 65 is disposed in the reaction chamber (chamber) 63, and a raw material gas is introduced into the quartz tube 65.
- a substrate table 66 is disposed in the quartz tube 65 so as to be rotatable and airtight.
- the substrate table 66 is provided with a heater 66h for heating the substrate.
- the temperature of the surface of the wafer 50 a during film formation is monitored by the infrared temperature monitor device 61 through a window 69 provided in the ceiling of the reaction chamber 63. This monitored temperature is a temperature at the time of growth or a temperature called a film forming temperature or a substrate temperature.
- the source gas is supplied by a pipe communicating with the quartz tube 65.
- the all-organometallic vapor phase growth method is characterized in that all source gases are supplied in the form of an organometallic gas. For this reason, the gradient composition can be formed with high accuracy.
- source gases such as impurities are not specified, but impurities are also introduced in the form of an organometallic gas.
- the raw material of the organometallic gas is put in a thermostat and kept at a constant temperature. Hydrogen (H 2 ) and nitrogen (N 2 ) are used as the carrier gas.
- the organometallic gas is transported by a transport gas, and is sucked by a vacuum pump and introduced into the quartz tube 65.
- the amount of carrier gas is accurately adjusted by an MFC (Mass Flow Controller). Many mass flow controllers, electromagnetic valves and the like are automatically controlled by a microcomputer. Therefore, the gradient composition of the InGaAs layer 3a and the GaAsSb layer 3b can be formed with high accuracy.
- MFC
- the n-type InP buffer layer 2 is epitaxially grown on the S-doped n-type InP substrate 1 to a film thickness of 150 nm.
- TeESi tetraethylsilane
- TMIn trimethylindium
- TBP tertiary butylphosphine
- the InP buffer layer 2 may be grown using an inorganic raw material PH 3 (phosphine). In the growth of the InP buffer layer 2, even if the growth temperature is about 600 ° C.
- the crystallinity of the InP substrate located in the lower layer is not deteriorated by heating at about 600 ° C.
- the substrate temperature is, for example, in the range of 400 ° C. or more and 560 ° C. or less. Need to be strictly maintained. The reason for this is that when heated above 560 ° C., the crystallinity of GaAsSb is greatly deteriorated due to heat damage, and when the InP window layer is formed at a temperature below 400 ° C., the decomposition efficiency of the source gas is increased.
- the buffer layer 2 may be an InP layer alone, but in a predetermined case, an n-type doped In 0.53 Ga 0.47 As layer is formed on the InP buffer layer with a thickness of 0.15 ⁇ m (150 nm). You may grow into. This In 0.53 Ga 0.47 As layer is also included in the buffer layer 2 in FIG.
- the type 2 MQW light-receiving layer 3 having InGaAs3a / GaAsSb3b with a gradient composition as a pair of quantum wells is formed.
- the film thicknesses of InGaAs3a and GaAsSb3b in the quantum well are preferably 3 nm or more and 10 nm or less, for example.
- the number of quantum wells is 50 to 300 pairs. However, since the type 2 transition is emphasized, the number is preferably about 200 to 250 pairs.
- triethylgallium (TEGa), tertiary butylarsine (TBAs) and trimethylantimony (TMSb) are used.
- the gradient of the composition y can be added by increasing TMSb while decreasing TBAs as the GaAsSb3b grows. Since the flow rate can be accurately adjusted with time by MFC, the formation of a composition gradient is easy.
- TEGa, TMIn, and TBAs can be used.
- Gradient application of In composition x can be performed by increasing or decreasing TEGa and TMIn in a complementary manner over time.
- These source gases are all organometallic gases, and the molecular weight of the compound is large. Therefore, it can be completely decomposed at a relatively low temperature of 400 ° C. or higher and 560 ° C. or lower and contribute to crystal growth. As a result, the temperature difference from the film formation temperature to room temperature can be reduced, the strain caused by the difference in thermal expansion of each material in the light receiving element 10 can be reduced, and the lattice defect density can be reduced. This is effective in suppressing dark current.
- the raw material for Ga (gallium) may be TEGa (triethylgallium) or TMGa (trimethylgallium).
- the raw material for In (indium) may be TMIn (trimethylindium) or TEIn (triethylindium).
- As (arsenic) TBAs (tertiary butylarsine) or TMAs (trimethylarsenic) may be used.
- Sb (antimony) may be TMSb (trimethylantimony), TESb (triethylantimony), TIPSb (triisopropylantimony), or TDMASb (tridimethylaminoantimony).
- a semiconductor element having a low MQW impurity concentration and excellent crystallinity can be obtained.
- a light receiving element with a small dark current and a high sensitivity can be obtained.
- the source gas is transported through the piping, introduced into the quartz tube 65, and exhausted. Any number of source gases can be supplied to the quartz tube 65 by increasing the number of pipes. For example, even a dozen kinds of source gases are controlled by opening and closing the electromagnetic valve.
- the flow rate of the source gas is controlled by a mass flow controller (MFC) shown in FIG. 5, and the flow into the quartz tube 65 is turned on and off by opening and closing the electromagnetic valve.
- MFC mass flow controller
- the quartz tube 65 is forcibly exhausted by a vacuum pump. There is no stagnation in the flow of the source gas, and it is performed smoothly and automatically. Therefore, the composition is switched quickly when forming the quantum well pair.
- MFC can be easily realized by controlling the film thickness according to the film thickness during the growth.
- the MFC controls, for example, TEIn (triethylindium) and TEGa (triethylgallium) while one TEIn decreases at a constant rate per time while the other TEGa While increasing accordingly, the sum of both may be kept constant, or only one raw material may be increased or decreased.
- TBAs tertiary butylarsine
- TIPSb triisopropylantimony
- the MFC may be controlled so as to keep the sum of the two constants while decreasing, or only one of the raw materials may be controlled to increase or decrease.
- the temperature distribution of the source gas does not have the directivity as on the inflow side or the outlet side of the source gas.
- the wafer 50a revolves on the substrate table 66, the flow of the source gas near the surface of the wafer 50a is in a turbulent state, and even the source gas near the surface of the wafer 50a contacts the wafer 50a. Except for the raw material gas, it has a large velocity component in the flow direction from the introduction side to the exhaust side. Therefore, most of the heat flowing from the substrate table 66 to the source gas through the wafer 50a is always exhausted together with the exhaust gas.
- the substrate temperature is heated to a low temperature range of 400 ° C. or more and 560 ° C. or less.
- the decomposition efficiency of the raw material is good, so that multiple quantum wells with the raw material gas flowing in a range very close to the wafer 50a
- the source gas that contributes to the growth of the structure is limited to one that is efficiently decomposed into the shape necessary for growth.
- the surface of the wafer 50a is set to a monitored temperature.
- the temperature suddenly decreases or a large temperature step is generated as described above. Therefore, in the case of a raw material gas having a decomposition temperature of T1 ° C., the substrate surface temperature is set to (T1 + ⁇ ), and ⁇ is determined in consideration of variations in temperature distribution and the like.
- T1 + ⁇ the substrate surface temperature
- ⁇ is determined in consideration of variations in temperature distribution and the like.
- the range is limited to the range of the thickness of the organic metal molecules corresponding to several from the surface. Therefore, organometallic molecules in the range in contact with the wafer surface and molecules located within the film thickness range of several organometallic molecules from the wafer surface mainly contribute to the crystal growth, and the outer organic molecules. It is considered that the metal molecules are discharged out of the quartz tube 65 with almost no decomposition. When the organometallic molecules near the surface of the wafer 50a are decomposed and crystal growth occurs, the organometallic molecules located outside enter the replenishment.
- the range of the organometallic molecules that can participate in crystal growth is limited to a thin source gas layer on the surface of the wafer 50a by making the wafer surface temperature slightly higher than the temperature at which the organometallic molecules decompose. it can.
- phase growth occurs in the GaAsSb layer of the multi-quantum well structure when grown in a temperature range exceeding 560 ° C., and the crystal growth surface of the multi-quantum well structure having clean and excellent flatness, and A multiple quantum well structure having excellent periodicity and crystallinity cannot be obtained.
- the growth temperature is set to a temperature range of 400 ° C. or higher and 560 ° C. or lower. is important.
- FIG. 6 is a flowchart of a method for manufacturing a light receiving element according to the present invention.
- an In 0.53 Ga 0.47 As diffusion concentration distribution adjusting layer 4 lattice-matched to InP is located on the type 2 MQW light receiving layer 3, and the In 0.53
- the InP window layer 5 is located on the Ga 0.47 As diffusion concentration distribution adjusting layer 4.
- the p-type region 6 is provided by selectively diffusing Zn of the p-type impurity from the opening of the selective diffusion mask pattern 36 provided on the surface of the InP window layer 5.
- a pn junction or a pi junction is formed at the tip of the p-type region 6.
- a reverse bias voltage is applied to the pn junction or pi junction to form a depletion layer, and the charge due to photoelectron conversion is captured, so that the brightness of the pixel corresponds to the amount of charge.
- the p-type region 6 or the pn junction or pi junction is the main part constituting the pixel.
- the p-side electrode 11 that is in ohmic contact with the p-type region 6 is a pixel electrode, and reads the above charges for each pixel with the n-side electrode 12 that is set to the ground potential.
- the selective diffusion mask pattern 36 is left as it is on the surface of the InP window layer around the p-type region 6. Further, a protective film such as SiON not shown is coated.
- the selective diffusion mask pattern 36 is left as it is when the p-type region 6 is formed and then exposed to the atmosphere except for this, and the InP window layer is exposed to the atmosphere except for the surface of the p-type region and the mask pattern. This is because a surface level is formed at the boundary with the surface of the region, and dark current increases.
- One point is to continue the growth in the same film forming chamber or quartz tube 65 by the all-metal organic vapor phase epitaxy method after the MQW is formed as described above until the InP window layer 5 is formed. That is, before the InP window layer 5 is formed, the wafer 50a is not taken out from the film forming chamber and the InP window layer 5 is not formed by another film forming method.
- the interfaces 16 and 17 are not regrowth interfaces. For this reason, the oxygen and carbon concentrations are both lower than a predetermined level, and charge leakage does not occur particularly at the intersection line between the p-type region 6 and the interface 17. Also, the lattice defect density can be kept low at the interface 16.
- a non-doped In 0.53 Ga 0.47 As diffusion concentration distribution layer 4 having a film thickness of 1.0 ⁇ m, for example, is formed on the MQW light-receiving layer 3.
- the In 0.53 Ga 0.47 As diffusion concentration distribution layer 4 allows Zn of p-type impurities to reach the MQW light-receiving layer 3 from the InP window layer 5 by a selective diffusion method.
- the In 0.53 Ga 0.47 As diffusion concentration distribution adjusting layer 4 may be arranged as described above, but may not be provided.
- a p-type region 6 is formed by the selective diffusion described above, and a pn junction or a pi junction is formed at the tip thereof. Even when In 0.53 Ga 0.47 As diffusion concentration distribution adjusting layer 4 is inserted, In 0.53 Ga 0.47 As has a small band gap energy, so even if it is non-doped, the electric resistance of the light receiving element Can be lowered. By reducing the electrical resistance, it is possible to improve the responsiveness and obtain a moving image with good image quality. On the In 0.53 Ga 0.47 As diffusion concentration distribution adjusting layer 4, the undoped InP window layer 5 is continuously formed by the all-organic metal vapor phase epitaxy method while the wafer 50 a is disposed in the same quartz tube 65.
- the growth temperature of the InP window layer 5 can be made 400 ° C. or more and 560 ° C. or less, and further 535 ° C. or less.
- the MQW GaAsSb located under the InP window layer 5 is not damaged by heat, and the MQW crystallinity is not impaired.
- the MQW containing GaAsSb is formed in the lower layer, it is necessary to strictly maintain the substrate temperature within a range of, for example, a temperature of 400 ° C. or higher and 560 ° C. or lower.
- the reason for this is that when heated above 560 ° C., the crystallinity of GaAsSb is greatly deteriorated due to heat damage, and when the InP window layer is formed at a temperature below 400 ° C., the decomposition efficiency of the source gas is increased. Since it significantly decreases, the impurity concentration in the InP window layer 5 increases, and the high quality InP window layer 5 cannot be obtained.
- the interface between the In 0.53 Ga 0.47 As diffusion concentration distribution adjusting layer and the InP window layer was a regrowth interface once exposed to the atmosphere.
- the regrowth interface is identified by satisfying at least one of an oxygen concentration of 1 ⁇ 10 17 cm ⁇ 3 or more and a carbon concentration of 1 ⁇ 10 17 cm ⁇ 3 or more by secondary ion mass spectrometry. be able to.
- the regrowth interface forms a crossing line with the p-type region, and a charge leak occurs at the crossing line, thereby significantly degrading the image quality.
- phosphine PH 3
- PH 3 phosphine
- the verified cases are the following three cases.
- In 0.53 Ga 0.47 As is a composition having a lattice mismatch of zero.
- Case 2 Middle of Table 1: Graded composition both GaAs 1-y Sb y layer 3b and In x Ga 1-x As layer 3a.
- the light receiving area is expanded to the long wavelength side by about 100 nm. Further, in case 3, the light receiving area expands to the long wavelength side by about 200 nm.
- an InGaAs / GaAsSb type 2 MQW lattice-matched to InP that can receive light up to an upper limit wavelength of 2 ⁇ m can be expanded to an upper limit wavelength of 2.2 ⁇ m by applying Case 3 belonging to the present invention.
- Such expansion of the upper limit wavelength can dramatically increase the usefulness depending on the wavelength of the absorption band in the inspection object.
- the light receiving sensitivity can be expanded to the long wavelength side of the near infrared without increasing the dark current, and depending on the inspection target, it can be a driving force for a dramatic increase in usefulness. .
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Abstract
Description
たとえば非特許文献1には、InP基板上に、InGaAs/GaAsSbのタイプ2のMQWを形成し、p型またはn型のエピタキシャル層によるpn接合によってカットオフ波長2.39μmのフォトダイオードが提案され、波長1.7μm~2.7μmの感度特性が示されている。
また、非特許文献2には、InGaAs5nmとGaAsSb5nmとを1ペアとして150ペア積層したタイプ2MQWの受光層を備える受光素子の波長1μm~3μmの感度特性(200K、250K、295K)が示されている。
すなわち、(1)第1の半導体層が、価電子帯が高いほうの層の場合は、受光の時、当該第1の半導体層の価電子帯の電子は、第2の半導体層の伝導帯へとタイプ2の遷移を行う。このとき当該第1の半導体層の価電子帯は、上述の組成の勾配によってエネルギ位置が高くなっているので、タイプ2の遷移におけるエネルギ差は小さくなる。結果、長波長側への受光感度の拡大がなされる。
また、(2)第1の半導体層が、価電子帯が低いほうの層の場合は、受光の時、当該第2の半導体層の価電子帯の電子が、第1の半導体層の伝導帯へとタイプ2の遷移を行う。このとき当該第1の半導体層の伝導帯は、上述の組成の勾配によってエネルギ位置が低くなっているので、タイプ2の遷移におけるエネルギ差は小さくなる。結果、長波長側への受光感度の拡大がなされる。
要は、第1の半導体層が、価電子帯が高いほうの層でもまたは価電子帯が低いほうの層でも、タイプ2の遷移におけるエネルギ差は小さくなり、感度の長波長化が実現する。
なお、第1の半導体層や第2の半導体層における、第1、第2は積層の順序などとは関係ない。たとえば「第1の」を「一方の」に、「第2の」を「他方の」に置き換えてもよい。また、第1の半導体層は、タイプ2の多重量子井戸構造のバンド構造において価電子帯が高いほうの層でも低いほうの層でもよい。
上記の構成によって、第2の半導体層においてもバンドギャップエネルギを小さくしてその最小化が実現する面を、第1の半導体層においてバンドギャップエネルギの最小化が実現している面と、接することができる。このバンドギャップエネルギ最小化が実現した面同士を接することで、当該界面では次のバンド構造が実現する。すなわち、価電子帯が高いほうの層におけるその価電子帯はエネルギ位置が高くなり、価電子帯が低いほうの層における伝導帯はエネルギ位置が低くなる。この結果、タイプ2の遷移を伴う受光が生じたとき、価電子帯が高いほうの層の価電子帯にいた電子は、価電子帯が低いほうの層の伝導帯に遷移して、エネルギ差の下限化が実現する。この界面をエネルギ差下限界面と呼ぶ。
第1および第2の半導体層において、上記下限界面と反対側の面では、組成勾配の付け方から、両方の層ともにバンドギャップエネルギは最大となる。この界面をエネルギ差上限界面と呼ぶ。エネルギ差下限界面とエネルギ差上限界面とは厚み方向に交互に位置する。
これによって、受光素子の感度の範囲を長波長側に拡大しながら、暗電流を低く抑制することができる。
これによって、各半導体層のIII―V族化合物半導体基板に対する平均的な格子不整合度を一定の範囲内に制限することができ、厚み方向に組成勾配を付けながらミスフィット転位の発生を防ぐことができる。
これによって、タイプ2の多重量子井戸構造において、価電子帯の高いほうの半導体層にGaAsSbなどのIII-V族化合物半導体を用いることができる。
これによって、タイプ2の多重量子井戸構造において、価電子帯の低いほうの半導体層にInGaAsなどのIII-V族化合物半導体を用いることができる。
これによって、タイプ2の多重量子井戸構造を形成する際、InGaAs層およびGaAsSb層の基板に対する平均的な格子不整合度を一定の範囲内に収めることが可能になり、ミスフィット転位を導入することなく容易に厚み方向に上述の組成勾配を付けることができる。
なお、InxGa1-xAs層における平均組成xaveが(0.38≦xave≦0.68)とは、「InxGa1-xAsという化学式の表示を有する化合物半導体層において、その中のxはその化合物半導体層内で厚み方向に勾配が付いていて、当然ながら、厚み方向にわたる平均値xaveが存在するが、その平均値xaveの範囲が、0.38≦xave≦0.68、である。」ということを示している。GaAs1-ySby層のyaveについても同様である。
上記のInxGa1-xAs層の平均組成範囲、およびGaAs1-ySby層における平均組成範囲を、端から端まで全範囲を利用した場合、上記の端面において3元系の化合物半導体とならない場合が生じる。そのような場合、たとえば端面でGaAsSbが形成されずにGaSbが形成される場合であっても、端面においてGaSb層を積層することになったとしても、1原子層程度であればミスフィット転位を導入することなく半導体層を成長することができる。また、暗電流を増大させることもない。従って上記端面における半導体結晶については、幅広く柔軟に解釈すべきである。
これによって入手が容易な大口径のInP基板を用いて、効率よく受光素子を大量生産することができる。
この方法によって、暗電流はそのままにして(増大させることなく)、受光域を長波長側に拡大することができる。
これによって、エネルギ差下限界面を簡単に形成することができ、タイプ2の遷移におけるエネルギ差を一層小さくすることができる。その場合、当然、エネルギ差上限界面も交互に形成される。このため平均組成は変化せず、実質的なバンドギャップエネルギも変化しないため、暗電流を低いままに維持することができる。
全有機金属気相成長法を用いることで、成長温度を下げることができ、良質のエピタキシャル積層体を得ることができる。また全有機金属気相成長法では、マスフローコントローラによって第1および第2の半導体層の各成分の供給量を調整して組成を意図するように変化させる。マスフローコントローラによる供給量の調整は高精度で正確なので、安定して再現性よく上述の勾配を付けることができる。
(InP基板1/InPまたはInGaAsバッファ層2/タイプ2(InGaAs/GaAsSb)MQWの受光層3/InGaAs拡散濃度分布調整層4/InP窓層5)
InP窓層5から深さ方向に延びるp型領域6は、SiN膜の選択拡散マスクパターン36の開口部から、p型不純物のZnを選択拡散することで形成する。受光素子10の周縁部の内側に、平面的に周囲限定されて拡散導入されるという形態は、上記SiN膜の選択拡散マスクパターン36を用いて選択拡散することによって達せられる。p型領域6にはAuZnによるp側電極11が、またInP基板1の裏面にはAuGeNiのn側電極12が、それぞれオーミック接触するように設けられている。この場合、InP基板1にはn型不純物がドープされ、所定レベルの導電性を確保されている。InP基板1の裏面には、またSiONの反射防止膜35を設け、InP基板の裏面側から光を入射する構造となっている。タイプ2MQWの受光層3には、上記のp型領域6の境界フロントにpn接合が形成され、上記のp側電極11およびn側電極12間に逆バイアス電圧を印加することにより、n型不純物濃度が低い側(n型不純物バックグラウンド)により広く空乏層を生じる。MQWの受光層3におけるバックグラウンドは、n型不純物濃度(キャリア濃度)で5×1015cm-3程度またはそれ以下である。そして、pn接合の位置は、多重量子井戸の受光層3のバックグラウンド(n型キャリア濃度)と、p型不純物のZnの濃度プロファイルとの交点で決まる。拡散濃度分布調整層4は、受光層3を構成するMQW内でのp型不純物の濃度分布を調整するために配置されるが、拡散濃度分布調整層4はなくてもよい。受光層3内では、Zn濃度は5×1016cm-3以下にするのがよい。
一方、GaAs1-ySby層3bの組成yは、厚み中央でy=0.49付近であり、また、平均組成yaveは、0.49であり、InPと格子整合しているが、界面Kに向かって組成yは0.54付近にまで上昇する。GaAs1-ySby層3bの層内では、組成yは界面Lでの0.43から界面Kにおける0.54付近へと増大する。
なお、図2では、組成x,yともに厚み方向にリニアに変化するように描いており、厚み中央での組成と平均組成が一致しているが、組成勾配の線形性は必須ではなく、ステップ状に増大してもよいし、波打ちながらまたはリップルを伴いながらマクロ的に組成の勾配が認められればよい。よって、厚み中央での組成と平均組成は必ずしも一致する訳ではない。
1.長波長化:
上記のMQWでは、半導体層においてバンドギャップエネルギが小さくなる組成勾配が付いた層の端面(上面または下面)で、そのバンドギャップエネルギは最も小さくなる。すなわち、その端面では、半導体層内で価電子帯は最も高いエネルギ位置をとり、かつ伝導帯は最も低いエネルギ位置をとる。このため、InxGa1-xAs層3aおよびGaAs1-ySby層3bの両方のバンドギャップエネルギが小さくなる端面が接する界面Kでは、価電子帯と伝導帯とが最も接近する。GaAs1-ySby層3bの価電子帯は、InxGa1-xAs層3aの価電子帯よりも高いエネルギ位置にあるので、上限の長波長の光を受光するとき、GaAs1-ySby層3bの価電子帯の電子がInxGa1-xAs層3aの伝導帯へとタイプ2の遷移をしてGaAs1-ySby層3bの価電子帯には正孔が生じる。このときの最小エネルギ差ΔEminを図3に示す。GaAs1-ySby層3bにおいて価電子帯が最も高くなる位置に正孔が存在する確率は、バンドのポテンシャル上(正孔に対しては上下逆のポテンシャルになる)、GaAs1-ySby層3bの層内では大きく、かつInxGa1-xAs層3aの伝導帯では最も低くなる位置に電子が位置する確率は、ポテンシャル上、InxGa1-xAs層3aの層内では大きい。このため、受光によって正孔/電子のペアが生成する確率は高くなる。換言すればこのタイプ2の受光効率は高い。
MQWを形成する半導体層の層内全体のバンドギャップエネルギが一様に小さくならなくても、図3に示すように半導体層の端の面付近でバンドギャップエネルギが小さくなれば、カットオフ波長は長波長側に確実に拡大される。言い換えれば、受光素子の受光域を長波長側に拡大することができる。
2.暗電流
図3に、半導体層3a,3bの平均組成に対応する価電子帯および伝導帯を破線で示す。この破線は、InPに格子整合する組成の場合のバンド構造の価電子帯または伝導帯とみることができる。図3によれば、各半導体層で最もバンドギャップエネルギが小さくなる端面と逆側の端面(すなわち界面L)では、バンドギャップエネルギは最も大きくなる。上記のように界面Kではバンドギャップエネルギは最も小さくなる。半導体層の平均組成に対応するバンドギャップがこの半導体層における平均的なバンドギャップエネルギである。暗電流は、この平均的なバンドギャップエネルギに対応して決まる。このため、半導体層の平均組成を基準として、暗電流を一定基準に保持しながら、一方の端面(エネルギ差下限界面K)でのバンドギャップの最小化によって長波長化を実現することができる。
バッファ層2は、InP層だけでもよいが、所定の場合には、そのInPバッファ層の上に、n型ドープしたIn0.53Ga0.47As層を、膜厚0.15μm(150nm)に成長してもよい。このIn0.53Ga0.47As層も図1中ではバッファ層2に含まれる。
また、InGaAs3aについては、TEGa、TMIn、およびTBAsを用いることができる。In組成xの勾配付与は、TEGaとTMInとを相補的に経時的に増減させて行うことができる。
これらの原料ガスは、すべて有機金属気体であり、化合物の分子量は大きい。このため、400℃以上かつ560℃以下の比較的低温で完全に分解して、結晶成長に寄与することができる。この結果、成膜温度から室温までの温度差を小さくすることができ、受光素子10内の各材料の熱膨張差に起因する歪を小さくでき、格子欠陥密度を小さく抑えることができる。これは暗電流の抑制に有効である。
原料ガスの流量は、図5に示すマスフローコントローラ(MFC)によって制御された上で、石英管65への流入を電磁バルブの開閉によってオンオフされる。そして、石英管65からは、真空ポンプによって強制的に排気される。原料ガスの流れに停滞が生じる部分はなく、円滑に自動的に行われる。よって、量子井戸のペアを形成するときの組成の切り替えは、迅速に行われる。
さらに、本発明の実施の形態では、基板温度を400℃以上かつ560℃以下という低温域に加熱される。このような低温域の基板表面温度でTBAsなどを原料とした全有機金属気相成長法を用いる場合、その原料の分解効率が良いので、ウエハ50aにごく近い範囲を流れる原料ガスで多重量子井戸構造の成長に寄与する原料ガスは、成長に必要な形に効率よく分解したものに限られる。
逆に考えると、ウエハ表面温度を有機金属分子が分解する温度よりほんのわずかに高くすることで、結晶成長に参加できる有機金属分子の範囲をウエハ50a表面上の薄い原料ガス層に限定することができる。
この多重量子井戸構造を形成する場合、560℃を超える温度範囲で成長すると多重量子井戸構造のGaAsSb層に相分離が起こり、清浄で平坦性に優れた多重量子井戸構造の結晶成長表面、および、優れた周期性と結晶性を有する多重量子井戸構造を得ることができない。このことから、成長温度を400℃以上かつ560℃以下という温度範囲にするが、この成膜法を全有機金属気相成長法にして、原料ガスすべてを分解効率の良い有機金属気体にすることが重要である。
図6は、本発明の受光素子の製造方法のフローチャートである。図1に示した受光素子10では、タイプ2MQWの受光層3の上には、InPに格子整合するIn0.53Ga0.47As拡散濃度分布調整層4が位置し、そのIn0.53Ga0.47As拡散濃度分布調整層4の上にInP窓層5が位置している。InP窓層5の表面に設けた選択拡散マスクパターン36の開口部からp型不純物のZnが選択拡散されてp型領域6が設けられる。そのp型領域6の先端部にpn接合またはpi接合が形成される。このpn接合またはpi接合に、逆バイアス電圧を印加して空乏層を形成して、光電子変換による電荷を捕捉して、電荷量に画素の明るさを対応させる。p型領域6またはpn接合もしくはpi接合は、画素を構成する主要部である。p型領域6にオーミック接触するp側電極11は画素電極であり、接地電位にされるn側電極12との間で、上記の電荷を画素ごとに読み出す。p型領域6の周囲の、InP窓層表面には、上記の選択拡散マスクパターン36がそのまま残される。さらに図示しないSiON等の保護膜が被覆される。選択拡散マスクパターン36をそのまま残すのは、p型領域6を形成したあと、これを除いて大気中に暴露すると、InP窓層においてp型領域の表面とマスクパターンを除いて大気中に暴露した領域の表面との境界に表面準位が形成され、暗電流が増大するからである。
上述のようにMQWを形成したあと、InP窓層5の形成まで、全有機金属気相成長法によって同じ成膜室または石英管65の中で成長を続けることが、一つのポイントになる。すなわち、InP窓層5の形成の前に、成膜室からウエハ50aを取り出して、別の成膜法によってInP窓層5を形成することがないために、再成長界面を持たない点が一つのポイントである。すなわち、InGaAs拡散濃度分布調整層4とInP窓層5とは、石英管65内において連続して形成されるので、界面16,17は再成長界面ではない。このため、酸素および炭素の濃度がいずれも所定レベル以下であり、とくにp型領域6と界面17との交差線において電荷リークが生じることはない。また界面16においても格子欠陥密度は低く抑えられる。
上記の選択拡散によってp型領域6が形成され、その先端部にpn接合またはpi接合が形成される。In0.53Ga0.47As拡散濃度分布調整層4を挿入した場合であっても、In0.53Ga0.47Asはバンドギャップエネルギが小さいのでノンドープであっても受光素子の電気抵抗を低くすることができる。電気抵抗を低くすることで、応答性を高めて良好な画質の動画を得ることができる。
In0.53Ga0.47As拡散濃度分布調整層4の上に、同じ石英管65内にウエハ50aを配置したまま連続して、アンドープのInP窓層5を、全有機金属気相成長法によってたとえば膜厚0.8μmにエピタキシャル成長するのがよい。原料ガスには、上述のように、トリメチルインジウム(TMIn)およびターシャリーブチルホスフィン(TBP)を用いる。この原料ガスの使用によって、InP窓層5の成長温度を400℃以上かつ560℃以下に、さらには535℃以下にすることができる。この結果、InP窓層5の下に位置するMQWのGaAsSbが熱のダメージを受けることがなく、MQWの結晶性が害されることがない。InP窓層5を形成するときには、下層にGaAsSbを含むMQWが形成されているので、基板温度は、たとえば温度400℃以上かつ560℃以下の範囲に厳格に維持する必要がある。その理由として、560℃を超えて加熱すると、GaAsSbが熱のダメージを受けて結晶性が大幅に劣化する点、および、400℃未満の温度としてInP窓層を形成すると、原料ガスの分解効率が大幅に低下するため、InP窓層5内の不純物濃度が増大し高品質なInP窓層5を得られない点があげられる。
本発明前は、In0.53Ga0.47As拡散濃度分布調整層とInP窓層との界面は、いったん大気に露出された再成長界面であった。再成長界面は、二次イオン質量分析によって、酸素濃度が1×1017cm-3以上、および、炭素濃度が1×1017cm-3以上、のうち、少なくとも一つを満たすことによって特定することができる。再成長界面は、p型領域と交差線を形成し、交差線で電荷リークを生じて、画質を著しく劣化させる。また、たとえばInP窓層を単なるMOVPE法(全有機ではない有機金属気相成長法)によって成長すると、燐の原料にホスフィン(PH3)を用いるため、分解温度が高く、下層に位置するGaAsSbの熱によるダメージの発生を誘起してMQWの結晶性を害することとなる。
(ケース1:表1の最上段):
GaAs1-ySby層3bに傾斜組成、しかし、InxGa1-xAs層3aはInPに格子整合するフラットな組成。本発明の実施の形態の説明における図4の構成に相当する。In0.53Ga0.47Asが、格子不整合度ゼロの組成である。
(ケース2:表1の中段):
GaAs1-ySby層3bおよびInxGa1-xAs層3aの両方に傾斜組成。ただしInxGa1-xAs層3aの層内におけるxのレンジは、0.48(Top)から0.58(Bottom)と控えめとした。このときのInGaAsの格子不整合度は±0.40%である。
(ケース3:表1の最下段):
GaAs1-ySby層3bおよびInxGa1-xAs層3aの両方に傾斜組成。ただしInxGa1-xAs層3aの層内におけるxのレンジは、0.43(Top)から0.63(Bottom)と大きくした。このときのInGaAsの格子不整合度は±0.66%である。
上記の3つのケースについて、受光域の波長上限(カットオフ波長=λmax)の長波長化の度合いを求めた。
結果を表1に示す。
Claims (11)
- III―V族化合物半導体による受光素子であって、
III―V族化合物半導体基板の上に位置し、第1の半導体層と第2の半導体層とが交互に積層されたタイプ2の多重量子井戸構造の受光層を備え、
前記第1の半導体層の層内において上面または下面へと、その第1の半導体層のバンドギャップエネルギが小さくなるように、厚み方向に組成の勾配が付いていることを特徴とする、受光素子。 - 前記第2の半導体層内において、前記第1の半導体層でバンドギャップエネルギが小さくなるように勾配が付された端の面に接する面へと当該第2の半導体層のバンドギャップエネルギが小さくなるように、厚み方向に組成の勾配が付いていることを特徴とする、請求項1に記載の受光素子。
- 前記組成の勾配が付された、第1の半導体層および第2の半導体層のうち少なくともいずれか一つの半導体層において、
前記バンドギャップエネルギが小さくなる極限位置の端面での組成は、それぞれの半導体層の平均組成に対して、格子定数の変化に換算して、格子不整合度が0.2%を超えることを特徴とする、請求項1または2に記載の受光素子。 - 前記第1の半導体層および第2の半導体層のうち少なくともいずれか一つの半導体層における平均組成は、格子定数の変化に換算して、前記III―V族化合物半導体基板との格子不整合度が±1%以内であることを特徴とする、請求項1~3のいずれか1項に記載の受光素子。
- 前記第1の半導体層および第2の半導体層のうち、価電子帯のポテンシャルエネルギが高いほうの半導体層に、Ga、AsおよびSbのうち少なくとも一つを含むことを特徴とする、請求項1~4のいずれか1項に記載の受光素子。
- 前記第1の半導体層および第2の半導体層のうち、価電子帯のポテンシャルエネルギが低いほうの半導体層に、In、GaおよびAsのうち少なくとも一つを含むことを特徴とする、請求項1~5のいずれか1項に記載の受光素子。
- 前記多重量子井戸構造が、InxGa1-xAsとGaAs1-ySbyとで形成されており、前記InxGa1-xAs層における平均組成xaveは(0.38≦xave≦0.68)であり、前記GaAs1-ySby層における平均組成yaveは(0.36≦yave≦0.62)であることを特徴とする、請求項1~6のいずれか1項に記載の受光素子。
- 前記III―V族化合物半導体基板がInP基板であることを特徴とする、請求項1~7のいずれか1項に記載の受光素子。
- III―V族化合物半導体による受光素子の製造方法であって、
InP基板の上に、第1の半導体層と第2の半導体層とを交互に積層してタイプ2の多重量子井戸構造の受光層を形成する工程を備え、
前記多重量子井戸構造の形成工程では、前記第1の半導体層の層内において上面または下面へと、その第1の半導体層のバンドギャップエネルギが小さくなるように、厚み方向に組成の勾配を付けることを特徴とする、受光素子の製造方法。 - 前記多重量子井戸構造の形成工程では、前記第2の半導体層内において、前記第1の半導体層でバンドギャップエネルギが小さくなるように勾配が付されている端に接する面へと当該第2の半導体層のバンドギャップエネルギが小さくなるように、厚み方向に組成の勾配を付けることを特徴とする、請求項9に記載の受光素子の製造方法。
- 全有機金属気相成長法により前記多重量子井戸構造を形成し、前記第1の半導体層、もしくは第1の半導体層および第2の半導体層に、前記組成の勾配を付けるとき、前記全有機金属気相成長法の成長機構に組み込まれているマスフローコントローラを調節することで、前記組成の勾配を付けることを特徴とする、請求項9または10に記載の受光素子の製造方法。
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JP2015082573A (ja) * | 2013-10-22 | 2015-04-27 | 住友電気工業株式会社 | エピタキシャルウエハおよびその製造方法 |
JP6130774B2 (ja) * | 2013-12-05 | 2017-05-17 | 日本電信電話株式会社 | 半導体素子とその作製方法 |
JP6036906B2 (ja) * | 2015-04-20 | 2016-11-30 | 住友電気工業株式会社 | 受光素子およびその製造方法 |
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