NITRIDE LIGHT-EMITTING ELEMENT
20250087971 ยท 2025-03-13
Inventors
- AKIO UETA (Shizuoka, JP)
- Takashi Kano (Shiga, JP)
- Hiroshi Ohno (Osaka, JP)
- Akihiko ISHIBASHI (Osaka, JP)
Cpc classification
H01S5/343
ELECTRICITY
International classification
H01S5/30
ELECTRICITY
H01S5/323
ELECTRICITY
Abstract
A nitride light-emitting element includes: a GaN substrate; an n-type semiconductor layer including an n-type nitride-based semiconductor, the n-type semiconductor layer being disposed on the GaN substrate; a p-type semiconductor layer including a p-type nitride-based semiconductor; an active layer including a nitride-based semiconductor containing Ga or In, the active layer being disposed between the n-type semiconductor layer and the p-type semiconductor layer; and a p-type electron barrier layer including Al, the p-type electron barrier layer being disposed between the active layer and the p-type semiconductor layer. The p-type electron barrier layer shows a composition distribution in which a position in a depth direction of the p-type electron barrier layer is taken as a horizontal axis, and a proportion of an Al element in a total amount of group III elements at each position is taken as a vertical axis. The composition distribution has maximum value A.sub.1. The maximum value A.sub.1 is 46 mol % or more. The composition distribution has a width La of a region including the maximum value A.sub.1 in which the proportion of the Al element is continuously 0.9 times or more maximum value A.sub.1. A ratio of the width La to a thickness Lm of the p-type electron barrier layer is 0.2 or less.
Claims
1. A nitride light-emitting element comprising: a GaN substrate; an n-type semiconductor layer including an n-type nitride-based semiconductor, the n-type semiconductor layer being disposed on the GaN substrate; a p-type semiconductor layer including a p-type nitride-based semiconductor; an active layer including a nitride-based semiconductor containing Ga or In, the active layer being disposed between the n-type semiconductor layer and the p-type semiconductor layer; and a p-type electron barrier layer including Al, the p-type electron barrier layer being disposed between the active layer and the p-type semiconductor layer, wherein the p-type electron barrier layer shows a composition distribution in which a position in a depth direction of the p-type electron barrier layer is taken as a horizontal axis, and a proportion of an Al element in a total amount of group III elements at each position is taken as a vertical axis, the composition distribution has a maximum value A.sub.1, the maximum value A.sub.1 is 46 mol % or more, the composition distribution has a width La of a region including the maximum value A.sub.1 in which the proportion of the Al element is continuously 0.9 times or more the maximum value A.sub.1, and a ratio of the width La to a thickness Lm of the p-type electron barrier layer is 0.2 or less.
2. The nitride light-emitting element according to claim 1, wherein the width La is 1.5 nm or less.
3. The nitride light-emitting element according to claim 1, wherein the maximum value A.sub.1 is 60 mol % or less.
4. The nitride light-emitting element according to claim 1, wherein the composition distribution has at least a first region in which the proportion of the Al element changes at a first change rate, a second region in which the proportion of the Al element changes at a second change rate, and a third region in which the proportion of the Al element changes at a third change rate in order from the p-type semiconductor layer toward the active layer, the second change rate is different from at least each of the first change rate and the third change rate, the second region has the maximum value A.sub.1, and the second region has a width of 1.0 nm or less.
5. The nitride light-emitting element according to claim 4, wherein the composition distribution further includes a fourth region in which the proportion of the Al element changes at a fourth change rate and a fifth region in which the proportion of the Al element changes at a fifth change rate located closer to the active layer than the third region and in order from the p-type semiconductor layer toward the active layer, and the fourth change rate is different from at least each of the third change rate and the fifth change rate.
6. The nitride light-emitting element according to claim 5, wherein the fourth region has a second maximum value A.sub.2 that is 30 mol % or more and 40 mol % or less.
7. The nitride light-emitting element according to claim 6, wherein a ratio of the second maximum value A.sub.2 to the maximum value A.sub.1 is 0.55 or more and 0.89 or less.
8. The nitride light-emitting element according to claim 4, wherein the first change rate is 7.0 mol %/nm or more and 31.1 mol %/nm or less.
9. The nitride light-emitting element according to claim 1, wherein the nitride light-emitting element includes a semiconductor laser.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF EMBODIMENT
[0028] In an AlGaN layer (for example, an Al.sub.0.35Ga.sub.0.65N layer) as disclosed in PTLs 2 and 3, it is difficult to set the slope of the Al composition of region X3 to 7 mol %/nm or more. As described above, region X3 is a region in which the Al composition changes on the p-type clad layer side of the electron barrier layer. This is considered to be because Al in the electron barrier layer has diffused into an upper layer during the growth of the p-type clad layer. Therefore, a trial production examination was conducted by changing the growth conditions of the p-type clad layer, such as changing the growth temperature of the p-type clad layer and the time (interruption time) from the formation of an Al.sub.0.35Ga.sub.0.65N layer to the start of the p-type clad layer growth. However, almost the same slope of the Al composition was obtained under any condition, and a region having a steep slope of 7 mol %/nm or more could not be obtained.
[0029] As a result of intensive studies by the present inventors, it has been found that a region in which the Al composition changes with a steep slope is obtained in the electron barrier layer by controlling the binding energy of the crystal of several atomic layers on the p-type semiconductor layer side of the electron barrier layer.
[0030] An object of the present disclosure is to provide a nitride light-emitting element that has an electron barrier layer with a steep slope of an Al composition on a p-type semiconductor layer side and is capable of a low-voltage operation.
Conventional Example
[0031] First, the Al.sub.0.35Ga.sub.0.65N layer described in PTL 2 will be described.
[0032] In the atom probe evaluation method, a measurement sample is processed into a sharp needle-shaped sample having a tip diameter of about 100 nm, and a positive voltage of about 10 kV is applied, so that a high electric field is generated at the most distal end of the sample, and an electric field evaporation phenomenon is generated. Ions electrovaporized from the sample are evaluated by a two-dimensional detector to identify ion species. Then, the individually detected ions are continuously detected and reconstructed in the depth direction to obtain a three-dimensional atomic distribution.
[0033] In the Al.sub.0.35Ga.sub.0.65N layer to be produced, as illustrated in
[0034] Next, a mechanism in which Al diffusion occurs on the p-type semiconductor layer side as illustrated in
[0035] As described above, in a case where Al atoms in the electron barrier layer diffuse into the upper p-type semiconductor layer region, the Al atoms need to break Al-N bonds to be free. The binding energy between the Al atom and the nitrogen atom is 2.95 eV, and the binding energy between the Ga atom and the nitrogen atom is 1.45 eV. Considering these two binding energies, the GaN bond is more likely to be broken. Therefore, in Al.sub.0.35Ga.sub.0.65N, it is considered that Ga atoms existing near Al atoms first break the bonds and become free. In a case where Ga atoms existing in the vicinity become free, the nitrogen atoms one level below to which the Al atoms and the (free) Ga atoms have been commonly bonded are also unstable because the bonds with the Ga atoms are broken. As a result, the unstable nitrogen atoms are also easily desorbed. Then, when the unstable N atoms bonded to the Al atoms are removed by desorption, each of the Al atoms themselves also loses one of the bonds, and the energy required to dissociate the bond decreases. That is, in a state of being bonded to the lower nitrogen atom with three bonds, the bond dissociation energy of Al of 2.95 eV3=8.85 eV decreases to 2.95 eV2=5.9 eV because one nitrogen atom is removed. Therefore, the Al atom itself becomes unstable and tends to be free. Note that, in the case of Al.sub.0.35Ga.sub.0.65N, 65% of the group III atoms are Ga atoms, and thus there is a high possibility that Ga atoms exist in atoms adjacent to the Al atoms (bonded to a common nitrogen atom). Therefore, the GaN bond around the Al atom is likely to collapse, and the Al atom is likely to be free. As a result, it is considered that Al is easily diffused into the upper p-type semiconductor layer.
[0036] Exemplary embodiments of the present invention will be described below with reference to drawings.
FIRST EXEMPLARY EMBODIMENT
Configuration of Nitride Light-Emitting Element
[0037]
[0038] In nitride semiconductor laser 100, n-type AlGaN clad layer 102, n-type GaN clad layer 103, n-side InGaN guide layer 104, InGaN/InGaN DQWs active layer 105, p-side InGaN guide layer 106, electron barrier layer 107 including p-type AlGaN, p-type AlGaN/GaN superlattice clad layer 108, and p-type GaN contact layer 109 are sequentially stacked on GaN substrate 101. Furthermore, a ridge structure is formed in p-type AlGaN/GaN superlattice clad layer 108 and p-type GaN contact layer 109 by photolithography and etching. Moreover, current block region 110 including SiO.sub.2 is provided on a ridge sidewall. Moreover, p-electrode 111 and n-electrode 112 are formed on p-type GaN contact layer 109 on top of the ridge and on GaN substrate 101, respectively. Note that, in the present exemplary embodiment, n-type AlGaN clad layer 102 and n-type GaN clad layer 103 correspond to an n-type semiconductor layer including an n-type nitride-based semiconductor. Furthermore, InGaN/InGaN DQWs active layer 105 corresponds to an active layer including a nitride-based semiconductor containing Ga or In. Moreover, p-type AlGaN/GaN superlattice clad layer 108 and p-type GaN contact layer 109 correspond to a p-type semiconductor layer including a p-type nitride-based semiconductor.
Method of Manufacturing Nitride Light-Emitting Element
[0039] A method for manufacturing nitride semiconductor laser 100 having the above structure will be specifically described.
[0040] Nitride semiconductor laser 100 having the structure of
[0041] First, GaN substrate 101 introduced into an MOCVD furnace before epitaxial growth is thermally cleaned at 1100 C. in a hydrogen and NH.sub.3 atmosphere. By the thermal cleaning, carbon-based dirt adhering to a surface of the substrate and an oxide film on the surface of the substrate are removed.
[0042] Thereafter, the temperature is raised to 1130 C., and n-type AlGaN clad layer 102 and n-type GaN clad layer 103 are sequentially grown by supplying respective source gases together with the carrier gas. A film thickness of n-type AlGaN clad layer 102 is 1.5 m, and an Al composition thereof is 2.6%. On the other hand, a film thickness of n-type GaN clad layer 103 is 250 nm. When these layers are formed, SiH.sub.4 is supplied during growth in order to achieve n-type conduction. As a result, Si is doped into the film at 1.010.sup.18 cm.sup.3. Next, the growth temperature is lowered to 840 C., and n-side InGaN guide layer 104 having an In composition of 2.6% is grown to 180 nm.
[0043] Subsequently, InGaN/InGaN DQWs active layer 105 is grown at the same temperature. InGaN/InGaN DQWs active layer 105 has a structure in which two InGaN layer well layers (thickness 2.8 nm, In composition 18%) are sandwiched between InGaN barrier layers (thickness 7 nm, In composition 3.4%).
[0044] p-side InGaN guide layer 106 (film thickness 150 nm, In composition 2.6%) is grown on InGaN/InGaN DQWs active layer 105. Next, the growth temperature is raised to 985 C., and p-type electron barrier layer 107 including AlGaN having a thickness of 3 nm and an Al composition of 40% and AlN having a thickness of 1 nm is formed. Moreover, p-type AlGaN/GaN superlattice clad layer 108 having a film thickness of 660 nm is formed by stacking a pair of an AlGaN layer having a thickness of 1.85 nm and an Al composition of 5.2% and a GaN layer having a thickness of 1.85 nm. Next, p-type GaN contact layer 109 having a film thickness of 60 nm is formed.
[0045] p-type electron barrier layer 107, p-type AlGaN/GaN superlattice clad layer 108, and p-type GaN contact layer 109 dope Mg in the film by supplying CP.sub.2Mg during growth to obtain p-type conduction. p-type electron barrier layer 107, p-type AlGaN/GaN superlattice clad layer 108, and p-type GaN contact layer 109 contain Mg of 1.010.sup.19 cm.sup.3, 2.010.sup.18 cm.sup.3 to 1.010.sup.19 cm.sup.3, and 2.010.sup.20 cm.sup.3, respectively.
[0046] Furthermore, p-electrode 111 and n-electrode 112 include Pd, Pt, and Au, and Ti, Pt, and Au, respectively. In the present first exemplary embodiment, in order to obtain an oscillation wavelength of 450 nm, the InGaN layer having a thickness of 2.8 nm and an In composition of 18% is used as a well layer of InGaN/InGaN DQWs active layer 105, but the In composition and the thickness may be adjusted in accordance with the oscillation wavelength of 420 nm to 460 nm. Furthermore, although the (average) Al composition of n-type AlGaN clad layer 102 and p-type AlGaN/GaN superlattice clad layer 108 is 2.6%, in order to confine light perpendicularly to InGaN/InGaN DQWs active layer 105, the Al composition and the film thickness may be adjusted within a range where the effective refractive index of the active layer is also small and the Al composition is 2.5% to 5%.
p-Type Electron Barrier Layer
[0047] p-type electron barrier layer 107 in the present first exemplary embodiment will be described.
[0048] As described above, p-type electron barrier layer 107 includes Al.sub.0.4Ga.sub.0.6N having a thickness of 3 nm and AlN having a thickness of 1 nm. In p-type electron barrier layer 107 obtained by such a design, as illustrated in
[0049] As a factor of suppressing the Al diffusion toward the p-type semiconductor layer side in p-type electron barrier layer 107 of the present first exemplary embodiment, the following mechanism is considered.
[0050]
[0051] Furthermore, the composition distribution includes first region a1, second region a2, third region a3, fourth region a4, and fifth region a5 from clad layer (p-type semiconductor layer) 108 toward active layer 105. First region a1 is a region in which the proportion of the Al element changes at a first change rate. Second region a2 is a region where the proportion of the Al element changes at a second change rate. Third region a3 is a region where the proportion of the Al element changes at a third change rate. Fourth region a4 is a region where the proportion of the Al element changes at a fourth change rate. Fifth region a5 is a region where the proportion of the Al element changes at a fifth change rate. Note that the second change rate is different from the first change rate and the third change rate, and the fourth change rate is at least different from the third change rate and the fifth change rate.
[0052] In the composition distribution, second region a2 and fourth region a4 are substantially flat. Maximum value A.sub.1 of the Al composition distribution exists in the second region. As described above, maximum value A.sub.1 is 55 mol %. Furthermore, a width of second region a2 is 1.0 nm. Moreover, the composition distribution has width La of a region including maximum value A.sub.1 in which the ratio of the Al element is continuously 0.9 times or more maximum value A.sub.1. Width La is 1.3 nm. Then, the ratio of width La to thickness Lm of p-type electron barrier layer 107, that is, La/Lm is 0.196. On the other hand, when the maximum value of fourth region a4 is defined as second maximum value A.sub.2, second maximum value A.sub.2 is 40 mol %. The width of second region a2 may be 1.0 nm or less.
[0053] In p-type electron barrier layer 107 of the present first exemplary embodiment, a region from start position Xs on the active layer side in p-type electron barrier layer 107 to second maximum value A.sub.2, that is, fifth region a5 and fourth region a4 mainly have a function of suppressing overflow of electrons injected into active layer 105. Therefore, when thickness Lm of p-type electron barrier layer 107 itself is too thin, the function as an electron barrier layer is deteriorated. Furthermore, since second region a2 including maximum value A.sub.1 has a high Al concentration, it is preferable that second region a2 is thin for a low-voltage operation of the nitride laser. Therefore, the width of the region having a high Al concentration, that is, above-described width La is preferably 1.5 nm or less, and the above-described La/Lm is preferably 0.2 or less. In order to further utilize the function as the electron barrier layer, the Al composition at second maximum value A.sub.2 is desirably 30 mol % or more and 40 mol % or less, and more preferably 35 mol % or more and 40 mol % or less. With this configuration, the interface steepness of the electron barrier layer on the second conductive side first semiconductor layer side can be greatly improved, and the operating voltage of the nitride light-emitting element can be reduced. The ratio of second maximum value A.sub.2 to maximum value A.sub.1 may be 0.55 or more and 0.89 or less.
Second Exemplary Embodiment
[0054] The structure of a nitride semiconductor laser according to a second exemplary embodiment is substantially the same as that of the first exemplary embodiment except for the configuration of p-type electron barrier layer 107.
[0055] In the present second exemplary embodiment, as illustrated in
[0056]
[0057] Furthermore, the composition distribution of the present second exemplary embodiment also includes first region a1, second region a2, third region a3, fourth region a4, and fifth region a5 from clad layer (p-type semiconductor layer) 108 toward active layer 105. First region a1 is a region in which the proportion of the Al element changes at a first change rate. Second region a2 is a region where the proportion of the Al element changes at a second change rate. Third region a3 is a region where the proportion of the Al element changes at a third change rate. Fourth region a4 is a region where the proportion of the Al element changes at a fourth change rate. Fifth region a5 is a region where the proportion of the Al element changes at a fifth change rate. The second change rate is at least different from the first change rate and the third change rate, and the fourth rate of change is at least different from the third rate change and the fifth change rate.
[0058] Also in the composition distribution, second region a2 and fourth region a4 are substantially flat. Maximum value A.sub.1 of the Al composition distribution exists in the second region. As described above, maximum value A.sub.1 is 54 mol %. Furthermore, a width of second region a2 is 0.4 nm. Moreover, in the present second exemplary embodiment, width La of a region including maximum value A.sub.1, in which the ratio of the Al element is continuously 0.9 times or more maximum value A.sub.1, is 1.2 nm. Then, the ratio of width La to thickness Lm of p-type electron barrier layer 107, that is, La/Lm is 0.194. That is, the above preferable range (La/Lm0.20) is satisfied. Moreover, when the maximum value of fourth region a4 is defined as second maximum value A.sub.2, second maximum value A.sub.2 is 40 mol %.
AlN Film Thickness of Electron Barrier Layer
[0059] In the first and second exemplary embodiments described above, the thin film AlN of 1.0 nm or less is grown on the p-type AlGaN/GaN superlattice clad layer 108 side of p-type electron barrier layer 107, so that Al diffusion to the p-type semiconductor layer side can be suppressed, and the slope of the Al composition can be set to 7 mol %/nm or more.
Average Binding Energy Control Of Electron Barrier Layer
[0060] It is considered that the change in the thickness of AIN changes the crystal binding energy of p-type electron barrier layer 107 on the p-type AlGaN/GaN superlattice clad layer 108 side to suppress the diffusion of Al. Therefore, the diffusion of Al of p-type electron barrier layer 107 into the p-type AlGaN/GaN superlattice clad layer (p-type semiconductor layer) 108 side can be expressed by a diffusion formula using the average binding energy in the crystal on the p-type AlGaN/GaN superlattice clad layer 108 side of p-type electron barrier layer 107 as the activation energy. Therefore, fitting was performed using Formula (1).
[0061] Here, L.sub.OFS represents a diffusion length of Al, and is a value inversely proportional to the slope of the Al composition. D.sub.A1 is a diffusion coefficient of Al, E.sub.OFS is an average binding energy of four atomic layers on the p-type AlGaN/GaN superlattice clad layer 108 side of p-type electron barrier layer 107, K is a Boltzmann constant, T is a growth temperature (985 C. in the present exemplary embodiment), and t is a growth time of p-type AlGaN/GaN superlattice clad layer 108.
[0062]
[0063] In the present exemplary embodiment, since conditions other than the configuration of p-type electron barrier layer 107 are not changed, Formula (1) can be simplified and can be considered as Formula (2) described below.
[0064]
[0065] In the present first and second exemplary embodiments, AlN is used for growing p-type electron barrier layer 107, but in order to realize a slope of the Al composition of 7 mol %/nm or more, it can be seen from
[0066] Here, A is the Al composition at a position of above-described second maximum value A.sub.2, and d is a thickness of the film to be grown for termination (however, 1 nm or less). Terminating the p-type AlGaN/GaN superlattice clad layer 108 side of p-type electron barrier layer 107 under the condition that Formula (3) is satisfied makes it possible to form p-type electron barrier layer 107 capable of reducing the operating voltage of the nitride laser.
[0067] Note that, in the above-described exemplary embodiment, the Al composition inclined region of p-type electron barrier layer 107 toward the active layer 105 side is not provided, but as disclosed in PTL 2, a region where the Al composition changes may be provided as indicated by X1 in
[0068] In the nitride light-emitting element of the present disclosure, the slope of the Al composition on the p-type semiconductor layer side of the electron barrier layer is steep, and a low-voltage operation is possible.
INDUSTRIAL APPLICABILITY
[0069] In the nitride light-emitting element of the present invention, the slope of the Al composition on the p-type semiconductor layer side of the electron barrier layer is made steep, the operating voltage of the nitride light-emitting element is reduced, and low power consumption operation is enabled. Therefore, the present invention can be applied to applications such as displays, processing machines, and in-vehicle headlights.
REFERENCE MARKS IN THE DRAWINGS
[0070] 100 nitride semiconductor laser [0071] 101 GaN substrate [0072] 102 n-type AlGaN clad layer [0073] 103 n-type GaN clad layer [0074] 104 n-side InGaN guide layer [0075] 105 InGaN/InGaN DQWs active layer [0076] 106 p-side InGaN guide layer [0077] 107 electron barrier layer [0078] 108 p-type AlGaN/GaN superlattice clad layer [0079] 109 p-type GaN contact layer [0080] 110 current block region [0081] 111 p-electrode [0082] 112 n-electrode