KR20090026299A - Nitride semiconductor light emitting element - Google Patents
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Abstract
At a completely different point of time from the prior art, a nitride semiconductor light emitting device having improved carrier injection efficiency from a p-type nitride semiconductor layer to an active layer by simple means is provided. On the sapphire substrate 1, a buffer layer 2, an undoped GaN layer 3, an n-type GaN contact layer 4, an InGaN / GaN superlattice layer 5, an active layer 6, an undoped InGaN layer 7 ), the p-type GaN-based contact layer 8 is laminated, and the p-electrode 9 is mesa-etched on the p-type GaN-based contact layer 8 to expose the n-type GaN contact layer 4. The n electrode 10 is formed. An intermediate semiconductor layer formed between the well layer closest to the p side of the active layer having a quantum well structure and the p-type GaN-based contact layer 8 includes an undoped InGaN layer 7 and the total film thickness of the intermediate semiconductor layer. By making 20 nm or less, the carrier injection efficiency to the active layer 6 can be improved.
Description
The present invention relates to a nitride semiconductor light emitting device having a quantum well structure and having an active layer composed of nitride including a well layer.
Background Art In recent years, short wavelength semiconductor lasers have been developed with a focus on application to high density optical disc recording and the like. As a short wavelength semiconductor laser, hexagonal compound semiconductors (hereinafter, simply referred to as nitride semiconductors) containing nitrogen such as GaN, AlGaN, InGaN, InGaAlN, GaPN and the like are used. LEDs using nitride semiconductors have also been developed.
Although the light emitting element of the MIS structure was used for the said nitride semiconductor light emitting element, since the i-type GaN type semiconductor of high resistance is laminated | stacked, it was a problem that light emission output was very low generally. In order to solve this problem, electron irradiation or annealing is performed on the i-type GaN-based semiconductor layer.
In addition, even in the case of a nitride semiconductor light-emitting device in which a p-type GaN-based semiconductor layer is formed, efforts have been made to increase the light emission output. For example, as shown in
Further, in
Patent Document 1: Japanese Patent Publication No. 2778405
(Tasks to be solved by the invention)
However, as in the prior art, the luminous efficiency is improved by improving the ohmic contact between the p-electrode and the p-type GaN contact layer, the film thickness of the p-type GaN contact layer, the p-type dopant, and the crystallinity of the p-type AlGaN cladding layer. Even if it improved, there was a limit to the improvement effect, and when it wanted to further improve luminous efficiency, there was no effective means.
The present invention was devised to solve the above-mentioned problems, and from a completely different viewpoint from the prior art, the carrier injection efficiency from the p-type nitride semiconductor layer to the active layer was improved by simple means, and the luminous efficiency was improved. It is an object to provide a nitride semiconductor light emitting device.
(Means to solve the task)
The nitride semiconductor light emitting device of the present invention is a nitride semiconductor light emitting device having a structure in which a well layer has an active layer having a quantum well structure composed of a nitride including In between a p-type nitride semiconductor layer and an n-type nitride semiconductor layer. And an undoped InGaN layer included in the intermediate semiconductor layer formed between the well layer disposed closest to the p side of the active layer and the p-type nitride semiconductor layer, wherein the total film thickness of the intermediate semiconductor layer is 20 nm or less. Make a point.
MEANS TO SOLVE THE PROBLEM The present inventors discovered that there exist a completely different means from the said prior art as a means of improving the hole injection efficiency from a p-type semiconductor layer to an active layer. That is, a part of the intermediate semiconductor layer formed between the well layer disposed at the position closest to the p side of the active layer and the p-type nitride semiconductor layer is composed of an undoped InGaN layer, and the total film thickness of the intermediate semiconductor layer is 20 nm or less. As a result, it was found that the hole injection efficiency from the p-type nitride semiconductor layer to the active layer changes rapidly.
In addition, when the intermediate semiconductor layer is composed of an active layer barrier layer and an undoped InGaN layer, the undoped InGaN layer may also be an In composition gradient layer whose In composition decreases toward the p-type nitride semiconductor layer. .
In addition, when Mg-doped p-type Al x GaN (0.02≤x≤O.15) is formed as part of the p-type nitride semiconductor layer, the hole carrier concentration is in the range of 2x10 17 cm -3 or more. It also makes a point.
In addition, the nitride semiconductor light-emitting device of the present invention, in addition to the above-mentioned point, when the In composition ratio of the well layer which is the active layer becomes 10% or more and the emission wavelength is long, from the end of film formation of the final well layer in the growth direction of the active layer. It is a summary that the sum total of the film-forming time whose growth temperature exceeds 950 degreeC is 30 minutes or less until the completion | finish of film-forming of the p-type contact layer formed in contact with a p electrode which is a part of p-type nitride semiconductor layer. InGaN is particularly thermally unstable, and if the above conditions are exceeded, there is a risk of decomposition. In the worst case, In is separated and the wafer becomes black.
(Effects of the Invention)
In the nitride semiconductor light emitting device of the present invention, a part of the intermediate semiconductor layer formed between the well layer closest to the p side of the active layer having a quantum well structure and the p-type nitride semiconductor layer is composed of an undoped InGaN layer. Since the total film thickness of is formed to be 20 nm or less, the injection efficiency of the holes into the active layer can be extremely increased, and the light emission efficiency is improved.
In the case where the intermediate semiconductor layer is composed of an active layer barrier layer and an undoped InGaN layer, the undoped InGaN layer is formed into an In composition gradient layer whose In composition decreases toward the p-type nitride semiconductor layer. This becomes easy to be injected and the luminous efficiency is improved.
Further, since p-type Al x GaN (0.02≤x≤0.15) is laminated on the intermediate semiconductor layer, and the hole carrier concentration due to the p-type impurity is formed to be 2 x 10 17 cm -3 or more, the hole injection amount into the active layer Can be taken sufficiently, and the luminous efficiency can be improved.
In addition, during the film formation time when the growth temperature exceeds 950 ° C from the end of film formation of the final well layer in the growth direction of the active layer to the end of film formation of the p-type contact layer formed in contact with the p-electrode which is a part of the p-type nitride semiconductor layer. Since the total is less than 30 minutes, especially in a nitride semiconductor light emitting device having a long emission wavelength, that is, an element having an In composition ratio of 10% or more in the well layer of the active layer, deterioration of the active layer can be prevented and high The luminous intensity can be maintained.
1 is a view showing a cross-sectional structure of a first nitride semiconductor light emitting device of the present invention.
2 is a diagram showing a layer structure near the active layer.
3 is a view showing a layer structure different from that of FIG. 2 near the active layer.
4 is a view showing a cross-sectional structure of a second nitride semiconductor light emitting device of the present invention.
Fig. 5 is a graph showing the relationship between the total film thickness of the intermediate semiconductor layer formed between the final well layer of the active layer and the p-type nitride semiconductor layer and the luminance of the nitride semiconductor light emitting device.
FIG. 6 is a diagram showing an emission spectrum when the film thickness of an undoped InGaN layer is 350 kPa. FIG.
FIG. 7 is a diagram showing an emission spectrum when the film thickness of an undoped InGaN layer is 120 kPa. FIG.
8 is a diagram showing a relationship between In composition of an undoped InGaN layer and luminance of a nitride semiconductor light emitting device.
9 is a diagram illustrating a state of band gap energy in the vicinity of an active layer.
It is a figure which shows the relationship between the relative ratio of In flow volume for every growth temperature, and the In composition ratio of an InGaN layer.
11 is a graph showing the relationship between the growth temperature of the InGaN layer and the In composition ratio.
12 is a conceptual diagram for calculating the EL integral relative strength.
Fig. 13 is a diagram showing a state in which the EL integral relative strength changes depending on the type of intermediate semiconductor layer formed between the last well layer of the active layer and the p-type nitride semiconductor layer.
Fig. 14 is a diagram showing a state in which the EL integral relative intensity changes depending on the kind of intermediate semiconductor layer formed between the last well layer of the active layer and the p-type nitride semiconductor layer.
FIG. 15 is a graph showing the relationship between the Al composition ratio of AlGaN and the luminance of the nitride semiconductor light emitting element. FIG.
Fig. 16 is a graph showing the relationship between AlGaN growth temperature and emission spectrum.
It is a figure which shows the state in which the value which integrated PL intensity changed with temperature.
FIG. 18 is a diagram illustrating a relationship between a growth temperature and an internal quantum efficiency of a p-type nitride semiconductor layer. FIG.
19 is a diagram showing a relationship between a growth time and internal quantum efficiency for each growth temperature of a p-type nitride semiconductor layer.
(Explanation of the sign)
1: sapphire substrate 2: buffer layer
3: undoped GaN layer 4: n-type GaN contact layer
5 InGaN /
6a: barrier layer 6b: barrier layer
6c: well layer 7: undoped InGaN layer
8: p-type GaN-based contact layer 9: p-electrode
10: n electrode 11: p-type AlGaN cladding layer
1 shows a cross-sectional view of an example of a first nitride semiconductor light emitting device of the present invention. On the
As described above, the n-type
The
The
2 illustrates the structure of the
Here, the barrier layer 6b has a non-doping or Si doping concentration of 5 × 10 16
As shown in Fig. 2, after forming the
In either case of FIGS. 2 and 3, the film thickness of the
3, when the
Fig. 5 shows the total film thickness (horizontal axis) of the last well layer in the growth direction of the active layer, that is, the intermediate semiconductor layer formed between the well layer disposed at the position closest to the p side of the active layer and the p-type nitride semiconductor layer, and the luminance of the light emitting element. The relationship between the (vertical axis) is shown. The light emission intensity (luminance) was measured by changing the film thickness of the intermediate semiconductor layer. The vertical axis is shown on the basis of the luminance at 250 Hz. Here, the total film thickness of the intermediate semiconductor layer corresponds to the total film thickness of the barrier layer 6a and the
This can be considered as follows. FIG. 6 shows the emission spectrum in the case of the film thickness of the
On the other hand, Fig. 7 shows the emission spectrum when the film thickness of the
Next, the structure of the 2nd nitride semiconductor light emitting element of this invention is shown in FIG. The same code | symbol as FIG. 1 shows the structure similar to FIG. The difference between the second nitride semiconductor light emitting device and the first nitride semiconductor light emitting device is that the p-type
In the second nitride semiconductor light emitting device (constitution of FIG. 4), the luminance was measured by changing the film thickness of the
8 shows the relationship between the In composition ratio of the
Next, the case where the
When the In composition is inclined, as shown in Fig. 9, since the band structure in the conduction band responsible for hole conduction lowers the potential toward the well layer, the holes are easily introduced, which is preferable. In addition, if the growth temperature is high, the residual electron concentration decreases. Therefore, the composition gradient of In is preferably produced by increasing the growth temperature.
Next, the manufacturing method of the said 1st and 2nd nitride semiconductor light emitting element is demonstrated. On the
First, the
As the target, for example, a sintered GaN target is used. Of course, a sintered compact target of AlN, AlGaN or InGaN can be used. However, when using a sintered compact target, in the InGaN sintered compact target, since it is a substance which In hardly enters, it is hard to determine a composition. Therefore, the sintered compact target of GaN, AlN, or AlGaN is preferable.
Next, as described above, the
Subsequently, the substrate temperature is raised to 1065 ° C., for example, an
Here, after forming the last barrier layer 6a in the structure of FIG. 2, after growing the
Next, in the case of the structure of FIG. 1, as a p-type GaN
After removing the native oxide film on the surface of the p-type GaN-based
After completion of the mesa etching, Al is formed as the n-
By the way, without forming the p-
Since the ZnO electrode is of a predetermined size, after etching to the p-type GaN-based
Thereafter, as described above, mesa etching is performed to form the
4, the p-type
Next, the manufacturing method of an undoped InGaN layer when the
However, as shown in FIG. 10, when it is going to cover the range of the composition ratio of In widely, only the control ratio of a trimethyl indium supply cannot control broadly the composition ratio of In. Fig. 10 shows the relationship between the trimethylindium flow rate relative ratio and the In composition ratio when InGaN is produced. The trimethyl indium flow rate relative ratio is a ratio of the respective TMI flow rates when a certain flow rate is arbitrarily determined and the flow rate is 1, and a graph is drawn for each specific growth temperature.
For example, when the TMI flow rate relative ratio becomes about 0.2 or less, it can be seen that the In composition suddenly changes toward 0, and it becomes difficult to control the In composition ratio in this range. Therefore, it is intended to simply form an In composition gradient layer having a wide range of composition ratios by using a region in which the composition ratio of In hardly changes even if the supply ratio of trimethyl indium is increased or decreased.
As can be seen from FIG. 10, when the growth temperature is made constant, the In composition ratio remains saturated even if the supply ratio of trimethyl indium is increased or decreased in the vicinity of the point S (about 1.3) of the TMI flow rate. It is.
Thus, for example, the point S is taken as the value of the relative TMI flow rate in the region where the composition ratio of In hardly changes, the TMI flow rate relative ratio is fixed at the point S, and In of the curve for each growth temperature corresponding to the point S is obtained. If the composition ratio is P1, P2, P3, P4, it is found that when the growth temperature is changed from 770 ° C to 840 ° C, at least the In composition ratio changes from P1 to P4, that is, from about 18.5% to about 8%. Can be.
Thus, when the TMI flow rate relative ratio is fixed at S point, FIG. 11 plots the In composition ratio at the time of changing a growth temperature from 770 degreeC to 840 degreeC, and further high temperature is shown in the graph. 11, the horizontal axis represents the growth temperature of undoped InGaN, and the vertical axis represents the In composition ratio of undoped InGaN.
In this manner, when the growth temperature is raised without changing the relative flow rate of the TMI, the width of the upper and lower portions of the In composition ratio can be widened, and the In composition gradient layer can be easily produced.
In the configuration of FIG. 1, and also having the structure of FIG. 2, after the
As described above, the range of the composition gradient curve shown in FIG. 10 is determined by the start point and the end point of the growth temperature, but the change in the In composition ratio of the In composition gradient layer is, for example, from 18% to 3%. In the case where it is desired to form continuously, the growth temperature may be changed to T1 to T2, and when the change in the In composition ratio is to be continuously formed to 3% to 0.5%, the growth temperature may be changed to T2 to T3. As described above, if the growth temperature is high, the residual electron concentration is decreased. Therefore, it is preferable to produce the In composition gradient layer by increasing the growth temperature, and it is also preferable to make the starting point of the growth temperature high.
By the way, in the structure of FIG. 1 or FIG. 4, the luminous efficiency at the time of using three types of structures as an intermediate semiconductor layer was compared. The curves of X1 to X3 all use the structure of FIG. 3, and the curve of X1 is a semiconductor layer in contact with the last well layer of the
For example, the PL intensity integrated value in the case of
Next, when the PL intensity integral value for the temperature parameter RT is called I (RT), the PL integral relative intensity is expressed by I (RT) / I (12K). Fig. 13 shows I (RT) / I (12K), where the vertical axis is the EL integral relative intensity (PL integral relative intensity), and the horizontal axis is the inverse of the absolute temperature and is an Arennius plot. T of (1000 / T) indicated in the description of the abscissa is absolute temperature and the unit is K (Kelvin). The above measurement and calculation were performed, and the graph of X1-X3 was obtained.
In FIG. 13, the one closer to zero in the horizontal axis corresponds to the direction in which the temperature rises. Therefore, even if it is close to 0 of the horizontal axis, the one where the value of the EL integral relative intensity is closer to 1 becomes better in light emission efficiency. The good luminous efficiency means that the hole injection efficiency from the p-type nitride semiconductor layer of the p-type GaN-based contact layer or the p-type AlGaN cladding layer is good, and the semiconductor is in contact with the last well layer of the
As can be seen from Fig. 13, since the curve of X3 shows the state of the highest luminous efficiency over the temperature of 12K to 290K, the semiconductor layer having the In composition gradient as the semiconductor layer in contact with the last well layer of the
On the other hand, curve Y2 of FIG. 14 has an intermediate semiconductor layer formed between the well layer disposed at the position closest to the p side of the
In the same manner as in Fig. 13, a graph is drawn with the EL axis relative intensity and the horizontal axis as 1000 / T. Comparing the curves Y1 and Y2, it can be seen that the closer to the room temperature, the more the injection efficiency of the hole increases on the Y2 side. This is because the film thickness of the
Next, as shown in Fig. 4, Fig. 15 shows the relationship between the Al composition, the hole carrier concentration, and the light emission intensity of the nitride semiconductor light emitting element in the configuration of Fig. 4 when the p-type
In general, when the Al composition of the p-type AlGaN is increased, the barrier height can be easily secured, but the band gap is increased, the impurity activation rate is reduced, and the carrier concentration is low even at the same impurity concentration. Since the enhancement of the carrier concentration determines a certain barrier height for the electrons, the range to be used appropriately is determined. The use range is Al x GaN (0.02? X ? 0.15). Within this range, it is understood that the carrier concentration should be at least 2 × 10 17 cm −3 or more if the luminescent intensity does not decrease to an extreme and finds a practically enduring state.
By the way, the growth of the p-type AlGaN cladding layer can be formed even at a substrate temperature of 950 ° C. However, in the case of p-type AlGaN, the crystallinity is improved to prevent the occurrence of carrier compensation effect and increase of the residual electron concentration, thereby increasing the hole concentration. In order to keep (carrier concentration) high, as mentioned above, the growth temperature of 1000 degreeC or more is preferable.
Fig. 16 shows a state in which crystallinity changes with growth temperature. The vertical axis represents photoluminescence intensity (arbitrary unit), and the horizontal axis represents emission wavelength. The vertical axis represents the measured photoluminescence intensity (PL intensity) and is relatively shown based on the peak intensity (peak intensity of GaN) of the PK portion shown in the drawing. This is a configuration in which undoped GaN is laminated on a sapphire substrate, and an AlGaN monolayer 2000 Å is laminated on this undoped GaN. The excitation light source was measured at an excitation intensity of 2.5 mW and a measurement temperature of 12 K using a He-Cd laser. . Where K is Kelvin representing the absolute temperature.
Although p-type AlGaN may be grown at a substrate temperature of 950 ° C, as shown in FIG. 16, when grown at a substrate temperature of 950 ° C, a phenomenon called deep level emission occurs. This indicates that the carrier compensation effect in AlGaN or the new level, that is, crystal defects, occurs in the band gap, resulting in a decrease in the hole concentration. On the other hand, when growing at a substrate temperature of 1010 ° C. to improve crystallinity, deep state light emission does not occur, so that the hole concentration is maintained as it is, and deterioration of the hole injection efficiency can be prevented. Therefore, in order to further improve the crystallinity of p-type AlGaN, it turns out that the growth temperature of 1000 degreeC or more is preferable.
As described in FIG. 16, in order to make the crystallinity of p-type AlGaN very good, the growth temperature of 1000 ° C. or higher is better. In order to produce, the growth temperature is preferably at least 950 ° C or higher. However, when Al X Ga Y N (where X + Y = 1, 0 ≦ X <1, 0 <Y ≦ 1) used for a p-type current injection layer is grown at a high temperature of 950 ° C. or higher, a good p-type Crystals exhibiting conductivity are obtained, but when fabricated at a temperature lower than 950 ° C., the imperfections of the crystals become very large, and the hole concentration does not improve due to the carrier compensation effect or the increase in the residual electron concentration, and the crystal exhibits good p-type conductivity. This is not obtained.
By the way, especially in the visible light LED which light-emits at the peak wavelength of 410 nm or more using nitride which is especially important industrially, although the In composition of the InGaN well layer 6c of the
This state is shown in FIG. As the nitride semiconductor light emitting device, the In composition ratio range of the
Fig. 17 shows how the light emitting efficiency of the nitride semiconductor light emitting device changes with the growth temperature of the p-type GaN-based contact layer or the p-type AlGaN cladding layer. For example, in the configuration shown in FIG. 1, the p-type GaN-based contact layer is a p-type GaN contact layer, the growth temperature is kept constant, and the growth time of the p-type GaN contact layer is 27 minutes to form a light emitting device. The internal quantum efficiency was measured, and the growth temperature of the p-type GaN contact layer was changed to measure the internal quantum efficiency for each growth temperature. The growth temperature was set at 880 ° C in the first measurement, 950 ° C in the second measurement, and 1010 ° C in the third measurement and 1060 ° C in the fourth measurement. In Fig. 17, the horizontal axis represents the growth temperature of the p-type GaN contact layer, and the vertical axis represents the internal quantum efficiency (%) of the light emitting device.
By the way, the internal quantum efficiency is obtained as follows. As shown in FIG. 12, PL (photoluminescence) integral intensity value (area of the curve of 12K of a figure) in the case of
The average of the PL intensity integrated values in the state with the best luminous efficiency is represented by I (12K), and this I (12K) is used as a reference. It is represented by internal quantum efficiency η = I (290 K) / I (12 K). Accordingly, the higher the internal quantum efficiency is, the better the light emission efficiency is and the higher the light emission intensity is.
As can be seen from FIG. 18 shown on the basis of the internal quantum efficiency obtained as described above, the emission efficiency deteriorates rapidly after exceeding 1010 ° C. Thus, as a growth temperature which does not deteriorate the InGaN well layer 6c of the
In Fig. 18, the growth time is fixed at 27 minutes, and since the relationship between the growth temperature and the growth time is not known, the following items were also measured. For example, in the configuration of FIG. 1, the nitride semiconductor light emitting device in which the p-type GaN-based
Here, the growth time from the completion of the formation of the well layer closest to the p side to the completion of the deposition of the p-type GaN contact layer means that the barrier layer 6a, the
Of the three measurement points shown in FIG. 19, the intermediate measurement point represents 27 minutes of growth time. As shown in the figure, when the growth temperature is 900 ° C., even though the growth time is long, the influence on the luminescence intensity is small. Can be. This is because if the InGaN well layer 6c of the
In addition, in the case of the nitride semiconductor light emitting device of the configuration shown in FIG. 4, the p-type AlGaN cladding layer is increased in addition to the configuration of FIG. 1, so that the growth temperature of the p-type AlGaN cladding layer is increased to 950 ° C. or more. The total of time should be within 30 minutes.
Although the In composition of the InGaN well layer 6c of the
However, the
By the way, in the manufacturing method mentioned above, in the case of the structure of FIG. 1, using a p-type GaN layer as the p-type GaN
In the configuration of FIG. 1, when the p-type InGaN contact layer is used, the film formation of the well layer closest to the p-type nitride semiconductor layer among the well layers of the
On the other hand, although the p-type
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WO2011081474A2 (en) * | 2009-12-31 | 2011-07-07 | 우리엘에스티 주식회사 | Semiconductor light emitting device, and preparation method thereof |
CN113574215A (en) * | 2019-03-28 | 2021-10-29 | 日本碍子株式会社 | Base substrate and method for manufacturing the same |
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WO2011081474A2 (en) * | 2009-12-31 | 2011-07-07 | 우리엘에스티 주식회사 | Semiconductor light emitting device, and preparation method thereof |
WO2011081474A3 (en) * | 2009-12-31 | 2011-11-03 | 우리엘에스티 주식회사 | Semiconductor light emitting device, and preparation method thereof |
CN113574215A (en) * | 2019-03-28 | 2021-10-29 | 日本碍子株式会社 | Base substrate and method for manufacturing the same |
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