Method to improve performances of tunnel junctions grown by metal organic chemical vapor deposition
12550481 ยท 2026-02-10
Assignee
Inventors
- David Hwang (WIndermere, FL, US)
- Matthew S. Wong (Santa Barbara, CA, US)
- Shuji Nakamura (Santa Barbara, CA, US)
Cpc classification
H10H20/811
ELECTRICITY
H10H20/01335
ELECTRICITY
H10H20/821
ELECTRICITY
H10H20/812
ELECTRICITY
H10H20/819
ELECTRICITY
International classification
H10H20/812
ELECTRICITY
H10H20/821
ELECTRICITY
Abstract
A device including an activated p-type layer comprising a III-Nitride based Mg-doped layer grown by vapor phase deposition or a growth method different from MBE. The p-type layer is activated through a sidewall of the p-type layer after the removal of defects from the sidewall thereby increasing a hole concentration in the p-type layer. In one or more examples, the device includes an active region between a first n-type layer and the p-type layer; a second n-type layer on the p-type layer; and a tunnel junction between the second n-type layer and the p-type layer, and the activated p-type layer has a hole concentration characterized by a current density of at least 100 Amps per centimeter square flowing between the first n-type layer and the second n-type layer in response to a voltage of 4 volts or less applied across the first n-type layer and the second n-type layer.
Claims
1. A device comprising: an activated p-type layer comprising a III-Nitride based magnesium doped (Mg-doped) layer grown by vapor phase deposition or a growth method different from molecular beam epitaxy (MBE), wherein the p-type layer is activated through a sidewall of the p-type layer after a removal of defects from the sidewall so as to increase a hole concentration in the p-type layer as compared to without the removal of the defects; and an active region or layer between a first III-Nitride n-type layer and the p-type layer; a second III-Nitride n-type layer on the p-type layer; and a tunnel junction between the second III-Nitride n-type layer and the p-type layer; and wherein the activated p-type layer has the hole concentration characterized by a current density of at least 100 Amps per centimeter square flowing between the first III-Nitride n-type layer and the second III-Nitride n-type layer in response to a voltage of 4 volts or less applied across the first III-Nitride n-type layer and the second III-Nitride n-type layer.
2. The device of claim 1, further comprising a light emitting device and a mesa comprising first the III-Nitride n-type layer, the second III-Nitride n-type layer, the p-type layer, and the active region, wherein the mesa has a light emitting top surface having an area of 60 microns squared or less.
3. The device of claim 2, wherein the area is 5 microns squared or less.
4. The device of claim 1, wherein the current density is at least 300 amps per centimeter square.
5. The device of claim 1, wherein the activated p-type layer has the hole concentration characterized by the device having a wall plug efficiency of at least 25%.
6. The device of claim 1, wherein the device comprises a light emitting diode, a laser, a solar cell, or a photodetector.
7. The device of claim 1, comprising a transistor.
8. The device of claim 1, comprising an electronic or optoelectronic device.
9. The device of claim 1, wherein the vapor phase deposition comprises metal organic chemical vapor phase deposition.
10. A device, comprising: a mesa; a first metal contact on the mesa, wherein the mesa comprises: a III-Nitride active region between a cathode contact layer and a p-type layer, wherein the cathode contact layer comprises a first III-Nitride n-type layer; a second III-Nitride n-type layer on the p-type layer forming a tunnel junction between the second III-Nitride n-type layer and the p-type layer; an n-type anode contact layer between the second III-Nitride n-type layer and the first metal contact; and a second metal contact on the cathode contact layer; wherein: the device emits electromagnetic radiation in response to a recombination of holes with electrons in the III-Nitride active region when an electric field or voltage is applied across the anode contact layer and the cathode contact layer using the first metal contact and the second metal contact, and the p-type layer has a chemically treated sidewall comprising a reduced number of defects of a type that: are formed during formation of the mesa by dry etching, and suppress diffusion of hydrogen, formed during growth of the p-type layer, out of the p-type layer during a thermal activation of the device, and the reduced number of defects increase a hole concentration and reduce a voltage across the anode contact layer and the cathode contact layer for a given current density flowing between the anode contact layer and the cathode contact layer.
11. The device of claim 10, wherein the reduced number of defects increase at least one of a light output power, an external quantum efficiency, or a wall plug efficiency of the device.
12. The device of claim 10, wherein the voltage is between 2.5 V and 4V for the current density of 20 Amps per centimeter square.
13. The device of claim 10, wherein the hole concentration in the p-type layer and an electron concentration in the first III-Nitride n-type layer are such that: an external quantum efficiency and a wall plug efficiency are in a range of 25%-60% for a current density in a range 2-70 Amps per centimeter square, and a top of the mesa has a surface area of 6060 microns squared or less.
14. The device of claim 10, wherein the device comprises a green light emitting diode, the electromagnetic radiation comprises has a power of at least 0.003 mW at a green wavelength.
15. The device of claim 10, wherein the reduced number of defects reduce a number of magnesium (Mg) acceptors in the p-type layer that are not thermally activated to activate Mg dopants passivated by hydrogen in the p-type layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
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DETAILED DESCRIPTION OF THE INVENTION
(24) In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration a specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
(25) Technical Description
First Example
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(28) Devices manufactured using the method include light emitting devices (e.g., micro-light-emitting device structures and lasers) and electronic devices.
REFERENCES FOR FIRST EXAMPLE
(29) The following references are incorporated by reference herein. .sup.1 X. A. Cao, S. J. Pearton, A. P. Zhang, G. T. Dang, F. Ren, R. J. Shul, L. Zhang, R. Hickman, and J. M. Van Hove, Appl. Phys. Lett. 75, 2569 (1999). .sup.2 D. Hwang, A. J. Mughal, M. S. Wong, A. I. Alhassan, S. Nakamura, and S. P. Denbaars, Appl. Phys. Express 11, 012102 (2018). .sup.3 E. C. Young, B. P. Yonkee, F. Wu, S. H. Oh, S. P. DenBaars, S. Nakamura, and J. S. Speck, Appl. Phys. Express 9, (2016). .sup.4 Y. Kuwano, M. Kaga, T. Morita, K. Yamashita, and K. Yagi, Jpn. J. Appl. Phys. 12, 8 (2013).
Second Example: Application to MicroLED
(30) In recent years, micro-light-emitting diodes (LEDs) have been gaining significant research attention for next-generation display and visible-light communication applications (1,2). There are a variety of approaches to realize full-color displays by employing red, green, and blue emitters (3-6). However, monolithic III-nitride-based LEDs are particularly interesting for near-eye display applications, since this approach will simplify the mass transfer process with high pixel-per-inch standards (7,8). Tunnel junction (TJ) contacts have been utilized extensively to provide better optical and electrical properties in different III-nitride devices (9-12). Two growth methods have been widely used to realize TJ structures in the III-nitride material system, namely molecular-beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD). MBE-grown TJs have successfully shown great device performances, but MBE lacks the practical scalability for mass production (13-15). On the other hand, MOCVD gives good scalability, but the hydrogen-rich growth environment is problematic and post-growth annealing is necessary for hydrogen diffusion to activate the p-GaN (13,16). In the case of LEDs, due to the small device sizes, lateral sidewall activation after dry etching has been used to activate the passivated p-GaN (17,18). Nevertheless, the voltage penalty due to incomplete activation remains the main drawback, which results in low wall-plug efficiency (WPE) for MOCVD-grown TJ devices, compared to devices with conventional current spreading contacts, such as indium-tin-oxide (ITO) (10,17).
(31) In this example, the optoelectrical advantages of employing chemical treatments before sidewall activation are demonstrated by LEDs with MOCVD-grown TJ contacts. The devices with chemical treatments prior to thermal annealing show a significant reduction in voltage penalty, where the voltage values are 5.43 V and 3.05 V at 20 A cm.sup.2 for the 2020 m.sup.2 devices without and with chemical treatments before activation, respectively. This method is effective for device dimensions ranging from 55 to 100100 m.sup.2. This indicates the voltage penalty issue in MOCVD-grown TJ contacts can be improved significantly not only from the conventional growth approaches but also from the fabrication aspect.
(32) Additionally, the optical and electrical performances of the devices with MOCVD-grown TJ contacts are compared to devices with ITO contacts. Although the 2020 m.sup.2 MOCVD-grown TJ device with chemical treatments results in a voltage penalty of 0.2 V compared to the ITO device, the MOCVD-grown TJ device provides improvements of 64% higher in peak external quantum efficiency (EQE) and 77% higher in peak WPE due to the substantial optoelectrical benefits. Thus, this example reveals the possibility of utilizing MOCVD-grown TJ structures in LEDs and other optoelectronic devices.
(33) 1. Device Structure and Fabrication
(34) The MOCVD-grown TJ structure was grown on commercial blue LED epitaxial structure on a sapphire substrate (peak wavelength of 465 nm at 20 A cm.sup.2) to minimize growth variation. The TJ structure consisted of 10 nm n.sup.++-GaN layer grown at 825 C. ([Si]=110.sup.20 cm.sup.3), 100 nm n-GaN layer grown at 900 C. ([Si]=410.sup.19 cm.sup.3), and nm of n.sup.+-GaN layer at 900 C. ([Si]=810.sup.19 cm.sup.3). Before growing the TJ structure, a 5 min buffered hydrofluoric acid (BHF) dip was performed (14). After the TJ growth, LEDs with seven device dimensions ranging from 55 to 100100 m.sup.2 were fabricated. The light-emitting areas were defined using reactive-ion etching with silicon tetrachloride (SiCl.sub.4) as the etching gas. Before thermal annealing for p-GaN activation, 0, 1, 2, 3, and 4 cycles of chemical treatments were performed on the devices. Each cycle of the chemical treatment comprised 5 min of phosphoric acid (H.sub.3PO.sub.4) at 60 C., 5 min ultraviolet-ozone (UVO) treatment using a UVO reactor (Jelight Model M-144AX), and 5 min BHF dip. The devices were annealed at 700 C. for 30 min under N.sub.2/O.sub.2 environment. An omnidirectional reflector (ODR) was deposited using ion beam deposition as a dielectric isolation layer, where the ODR consisted of three periods of alternating layers of silicon dioxide (SiO.sub.2) and tantalum pentoxide, and aluminum oxide as a capping layer. After the ODR deposition, 50 nm of SiO.sub.2 was deposited using atomic layer deposition for sidewall passivation. A window was opened for metal deposition using BHF, and common metal contacts of 500/100/500 nm of Al/Ni/Au were deposited. A reference set of LEDs with 110 nm of ITO contact were fabricated with a similar method, where the detailed fabrication steps have been reported elsewhere (19).
(35) b. Device Characterization
(36) After device processing, the electrical characteristics were collected by on-wafer testing. For the measurements of light output power (LOP) and efficiency, the devices were singulated and packaged onto silver headers with encapsulation (Dow Corning OE-6650 resin), and the measurements were carried out in a calibrated integrating sphere. Sidewall activation is critical for MOCVD-grown TJ LEDs, because hydrogen diffusion is only possible at sidewalls and the diffusion barrier in n-GaN is high due to the preferred H.sup. state in n-type material as opposed to the favored H.sup.+ state in the p-type material (20). However, sidewall activation is typically performed after dry etching, where the plasma-induced sidewall damage is introduced into the device structure (21,22). The etch damage may produce either mid-level defects or n-type materialboth provide upward band bending from the interior p-type material and thus present a diffusion barrier for hydrogen (21-24) Thus, the sidewall damage due to dry etching must be removed before sidewall activation.
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(38) The effectiveness of the number of cycles for the chemical treatments before activation can be determined by the current densityvoltage characteristics of the 2020 m.sup.2 devices, as shown in
(39) The additional number of chemical treatment cycles provides oxygen at the sidewalls, where oxygen acts as a donor in the p-GaN and converts to n-type, and hence immoderate use of chemical treatments would result in more resistive characteristic than the optimal condition (24,29). A key feature of sidewall activation is related to the device size. Larger device dimensions require longer activation time for hydrogen diffusion, since more time is needed for hydrogen to diffuse to the sidewalls 18)
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(41) c. Comparison of TJ and ITO contacts
(42) To examine the practical usage of the MOCVD-grown TJ devices, the device performances with TJ and ITO contacts are compared. The electrical and optical characteristics of the 2020 m.sup.2 devices are presented in
(43) By separately analyzing the electrical and optical performances of the LEDs, TJ and ITO contacts offered different benefits. As a result, it is essential to determine the EQE and WPE of the devices.
(44) In conclusion, the electrical properties of LEDs with MOCVD-grown TJ contacts were significantly enhanced by employing chemical treatments before sidewall activation. The applied chemical treatments removed damaged sidewall material that inhibited efficient activation of the p-GaN. The 2020 m.sup.2 devices yielded 0.2 V voltage penalty at 20 A cm.sup.2, compared to ITO devices, and that is comparable to TJ structure grown by MBE. The TJ devices showed more than 40% and 30% improvements in LOP at 20 and 60 A cm.sup.2. Due to the high LOP, the TJ device resulted in 64% and 77% improvements in the peak EQE and WPE, respectively. This work demonstrates that MOCVD-grown TJ structures can be utilized in LEDs while exhibiting outstanding optical and electrical characteristics and achieving efficiency better than conventional ITO current spreading contacts.
REFERENCES FOR SECOND EXAMPLE
(45) The following references are incorporated by reference herein. 1) M. S. Wong, S. Nakamura, and S. P. DenBaars, ECS J. Solid State Sci. Technol. 9, 015012 (2020). 2) Y. Huang, E. Hsiang, M. Deng, and S. Wu, Light: Sci. Appl. 9, 105 (2020). 3) J.-T. Oh et al., Opt. Express 26, 11194 (2018). 4) M. S. Wong et al., Opt. Express 28, 5787 (2020). 5) Y. Lin, Y. Lu, W. Guo, C.-F. Lee, S.-W. Huang Chen, H.-C. Kuo, S. Liang, C.-W. Sher, T. Wu, and Z. Chen, Appl. Sci. 8, 1557 (2018). 6) H.-Y. Lin, C.-W. Sher, D.-H. Hsieh, X.-Y. Chen, H.-M. P. Chen, T.-M. Chen, K.-M. Lau, C.-H. Chen, C.-C. Lin, and H.-C. Kuo, Photonics Res. 5, 411 (2017). 7) S. Ichikawa, K. Shiomi, T. Morikawa, D. Timmerman, Y. Sasaki, J. Tatebayashi, and Y. Fujiwara, Appl. Phys. Express 14, 031008 (2021). 8) Y. Robin, F. Hemeret, G. DInca, M. Pristovsek, A. Trassoudaine, and H. Amano, Jpn. J. Appl. Phys. 58, SCCCO6 (2019). 9) E. Vadiee et al., Appl. Phys. Express 11, 082304 (2018). 10) K. W. Hamdy, E. C. Young, A. I. Alhassan, D. L. Becerra, S. P. DenBaars, J. S. Speck, and S. Nakamura, Opt. Express 27, 8327 (2019). 11) J. A. Kearns, J. Back, D. A. Cohen, S. P. DenBaars, and S. Nakamura, Opt. Express 27, 23707 (2019). 12) S. Lee, C. A. Forman, J. Kearns, J. T. Leonard, D. A. Cohen, S. Nakamura, and S. P. DenBaars, Opt. Express 27, 31621 (2019). 13) E. C. Young, B. P. Yonkee, F. Wu, S. H. Oh, S. P. DenBaars, S. Nakamura, and J. S. Speck, Appl. Phys. Express 9, 022102 (2016). 14) B. P. Yonkee, E. C. Young, S. P. DenBaars, S. Nakamura, and J. S. Speck, Appl. Phys. Lett. 109, 191104 (2016). 15) B. P. Yonkee, E. C. Young, C. Lee, J. T. Leonard, S. P. DenBaars, J. S. Speck, and S. Nakamura, Opt. Express 24, 7816 (2016). 16) S. Nakamura, T. Mukai, M. Senoh, and N. Iwasa, Jpn. J. Appl. Phys. 31, L139 (1992). 17) D. Hwang, A. J. Mughal, M. S. Wong, A. I. Alhassan, S. Nakamura, and S. P. Denbaars, Appl. Phys. Express 11, 012102 (2018). 18) Y. Kuwano, M. Kaga, T. Morita, K. Yamashita, K. Yagi, M. Iwaya, T. Takeuchi, S. Kamiyama, and I. Akasaki, Jpn. J. Appl. Phys. 12, 08JK12 (2013). 19) M. S. Wong, D. Hwang, A. I. Alhassan, C. Lee, R. Ley, S. Nakamura, and S. P. DenBaars, Opt. Express 26, 21324 (2018). 20) J. Neugebauer and C. G. Van De Walle, Appl. Phys. Lett. 68, 1829 (1996). 21) X. A. Cao, S. J. Pearton, A. P. Zhang, G. T. Dang, F. Ren, R. J. Shul, L. Zhang, R. Hickman, and J. M. Van Hove, Appl. Phys. Lett. 75, 2569 (1999). 22) J. M. Lee, K. M. Chang, S. W. Kim, C. Huh, I. H. Lee, and S. J. Park, J. Appl. Phys. 87, 7667 (2000). 23) J. Kou, C.-C. Shen, H. Shao, J. Che, X. Hou, C. Chu, K. Tian, Y. Zhang, Z.-H. Zhang, and H.-C. Kuo, Opt. Express 27, 643 (2019). 24) C. Le Maoult, D. Vaufrey, F. Martin, E. Martinez, E. Nolot, S. Cadot, and E. Gheeraert, Proc. SPIE 11280, 112801C (2020). 25) M. S. Wong, C. Lee, D. J. Myers, D. Hwang, J. A. Kearns, T. Li, J. S. Speck, S. Nakamura, and S. P. Denbaars, Appl. Phys. Express 12, 097004 (2019).
Third Example: Comparative Study
(46) In this example, the optoelectrical performances of blue and green TJ LEDs with three activation methods are compared at different activation temperatures ranging from 670 to 790 C. in 30 C. increments. From the optical features, the devices with chemical treatment before sidewall activation exhibited uniform electroluminescence (EL) at 1 A/cm.sup.2, whereas the devices with sidewall activation without chemical treatment or with the SAG design exhibited inhomogeneous EL patterns. Moreover, the LOP of the 2020 m.sup.2 blue devices with chemical treatment was 15% higher than that of the SAG devices at 100 A/cm.sup.2. In the optical performance, the blue LEDs showed smaller degradation in LOP with increasing temperatures than the green devices, and the reduction in LOP for both devices was more significant for activation temperature above 730 C.
(47) In the electrical performance, the 55 m.sup.2 devices with chemical treatment or SAG showed superior operating voltage at 20 A/cm.sup.2 at all activation temperatures, while the voltage penalty decreased gradually with activation temperature for devices with only sidewall activation. Due to the greater LOP and similar electrical performances, the 5 LEDs with chemical treatment before activation yielded higher external quantum efficiency (EQE) and wall-plug efficiency (WPE) at low current density than the devices with SAG, and the enhancements were observed in both 2020 and 6060 m.sup.2 devices.
(48) 1. Device Structure and Fabrication
(49) Commercial blue (467 nm) and green (532 nm) InGaN LED epitaxial structure with a 20 nm of p.sup.+-contact layer ([Mg] 910.sup.19 cm.sup.3) and a 40 nm of p-layer ([Mg] 119 cm.sup.3) on sapphire substrates were used to minimize material variation. The TJ structure that consisted of 10 nm n.sup.++-GaN layer ([Si] 110.sup.20 cm.sup.3), 100 nm n-GaN layer ([Si] 410.sup.19 cm.sup.3), and 10 nm of n.sup.+-GaN layer ([Si] 810.sup.19 cm.sup.3) was grown by MOCVD. The detailed device fabrication with sidewall passivation using atomic-layer deposition has been reported in the literature [12-14]. Devices ranging from 55 to 100100 m.sup.2 were treated with 0 (reference) or 3 cycles (3-cycle) of chemical treatment before thermal activation, where each cycle of the chemical treatment consisted of 5-minute of phosphoric acid at 60 C., 5-min of ultraviolet-ozone treatment, and 5-min hydrofluoric acid dip, or were regrown using a SiO.sub.2 hard mask (SAG) [11,13,15]. Thermal activation was performed with an AET RX6 rapid thermal processer under N.sub.2/O.sub.2 ambient at 670, 700, 730, 760, or 790 C. for 30 min. All devices were fabricated together to avoid potential processing variations. The electrical and optical data were collected by on-wafer measurements, and the efficiency performance was found from singulated devices mounted and encapsulated on silver headers and measured in an integrating sphere [4,14].
(50) All methods employ unique activation mechanisms, where the reference devices take advantage of activation through the device sidewalls and the activation barriers, such as nitrogen vacancies or plasma damage, are mitigated by utilizing chemical treatment before sidewall activation for the 3-cycle devices. The main difference between the SAG devices and the other two sets of devices is the holes in the SAG devices, where the openings serve as a window for hydrogen diffusion from the surface of the p-GaN layer during activation. In this case, the SAG devices have a hole diameter of 2 m, with a pitch distance less than 10 m to ensure complete activation [12].
(51) In addition to the EL emission profiles, the optical characteristics of the devices showed significant contrasts between the different TJ activation methods. The following optical comparisons focus on the SAG devices and the 3-cycle devices.
(52) Other than the TJ activation method, the activation temperature serves as an important factor to the overall MOCVD-grown TJ device performance, as optimizing the temperature is crucial to minimize the voltage penalty while protecting the active region.
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(54) This reduction in voltage penalty was attributed to the increasing effective hydrogen diffusion length with the increasing temperature, where high temperature either reduced activation barriers or provided more energy for diffusion to take place. For the 3-cycle devices, the operating voltage in the 55 m.sup.2 devices was almost identical to that of the SAG devices as presented in
(55) The performances of devices employing chemical treatment before activation have been improved in terms of the optical and electrical aspects, and the benefits can also be observed in the EQE and WPE characteristics.
(56) In conclusion, the optoelectrical effects of three MOCVD-grown TJ activation techniques on InGaN based blue and green LEDs were analyzed. The 3-cycle devices demonstrated homogeneous EL emission profiles, while the reference and SAG devices showed nonuniform emission profiles due to insufficient current injection. The 3-cycle devices yielded higher LOP compared to the SAG devices with the increase being higher at low current densities. The enhancement was partially attributed to the reduction in SRH non-radiative recombination sites using chemical treatment. Additionally, the operating voltage between the 55 m.sup.2 SAG devices and the 3-cycle devices showed almost identical performance, suggesting that both sets of devices yielded complete activation for devices smaller than 4040 m.sup.2. Green devices using all three TJ activation methods exhibited significant drop in LOP for temperatures above 730 C., suggesting that the maximum activation temperature was limited by the degradation temperature in the active region. The 3-cycle devices also resulted in higher EQE and WPE than the SAG devices due to the higher LOP characteristic. This indicates that the use of chemical treatment before thermal activation is important for micrometer-scale devices with MOCVD-grown TJ contacts to yield outstanding electrical and optical performances.
REFERENCES FOR THIRD EXAMPLE
(57) The following references are incorporated by reference herein. 1 M. S. Wong, S. Nakamura, and S. P. DenBaars, ECS J. Solid State Sci. Technol.9, 015012 (2020). 2 Y. Huang, E. L. Hsiang, M. Y. Deng, and S. T. Wu, Light: Sci. Appl. 9, 105 (2020). 3 Y. Lin, Y. Lu, W. Guo, C.-F. Lee, S.-W. Huang Chen, H.-C. Kuo, S. Liang, C.-W. Sher, T. Wu, and Z. Chen, Appl. Sci. 8, 1557 (2018). 4 M. S. Wong, J. A. Kearns, C. Lee, J. M. Smith, C. Lynsky, G. Lheureux, H. Choi, J. Kim, C. Kim, S. Nakamura, J. S. Speck, and S. P. DenBaars, Opt. Express 28, 5787 (2020). 5 Y. Robin, F. Hemeret, G. DInca, M. Pristovsek, A. Trassoudaine, and H. Amano, Jpn. J. Appl. Phys., Part 1 58, SCCCO6 (2019). 6Z. Liu, C. Lin, B. Hyun, C. Sher, Z. Lv, B. Luo, F. Jiang, T. Wu, C. Ho, H. Kuo, and J. He, Light: Sci. Appl. 9, 1 (2020). 7M. S. Wong, S. Nakamura, and S. P. DenBaars, High External Quantum Efficiency III-Nitride Micro-Light-Emitting Diodes, 1st ed. (Elsevier, Inc., 2021). 8E. C. Young, B. P. Yonkee, F. Wu, S. H. Oh, S. P. DenBaars, S. Nakamura, and J. S. Speck, Appl. Phys. Express 9, 022102 (2016). 9S. Lee, C. A. Forman, J. Kearns, J. T. Leonard, D. A. Cohen, S. Nakamura, and S. P. DenBaars, Opt. Express 27, 31621 (2019). 10 J. Back, M. S. Wong, J. Kearns, S. P. DenBaars, C. Weisbuch, and S. Nakamura, Opt. Express 28, 29991 (2020). 11 D. Hwang, A. J. Mughal, M. S. Wong, A. I. Alhassan, S. Nakamura, and S. P. Denbaars, Appl. Phys. Express 11, 012102 (2018). 12 P. Li, H. Zhang, H. Li, M. Iza, Y. Yao, M. S. Wong, N. Palmquist, J. S. Speck, S. Nakamura, and S. P. DenBaars, Opt. Express 28, 18707 (2020). 13 M. S. Wong, J. Back, D. Hwang, C. Lee, J. Wang, S. Gandrothula, T. Margalith, J. S. Speck, S. Nakamura, and S. P. DenBaars, Appl. Phys. Express 14, 086502 (2021). 14 M. S. Wong, D. Hwang, A. I. Alhassan, C. Lee, R. Ley, S. Nakamura, and S. P. DenBaars, Opt. Express 26, 21324 (2018). 15 P. Li, H. Zhang, H. Li, Y. Zhang, Y. Yao, N. Palmquist, M. Iza, J. S. Speck, S. Nakamura, and S. P. 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The subject matter of this document was made by or originated from one or more members of the inventive entity of this patent application entitled METHOD TO IMPROVE PERFORMANCES OF TUNNEL JUNCTIONS GROWN BY METAL ORGANIC CHEMICAL VAPOR DEPOSITION,, which application claims priority to U.S. Provisional Patent Application No. 63/154,262, filed Feb. 26, 2021, by David Hwang, Matthew S. Wong, and Shuji Nakamura, entitled METHOD TO IMPROVE PERFORMANCES OF TUNNEL JUNCTIONS GROWN BY MOCVD,. 26. Matthew S. Wong, Nathan C. Palmquist, Jiaxiang Jiang, Philip Chan, Changmin Lee, Panpan Li, Ji Hun Kang, Yong Hyun Baek, Chae Hon Kim, Daniel A. Cohen, Tal Margalith, James S. Speck, Shuji Nakamura, and Steven P. DenBaars, Effects of activation method and temperature to III-nitride micro-light-emitting diodes with tunnel junction contacts grown by metalorganic chemical vapor deposition Appl. Phys. Lett. 119, 202102 (2021); doi: 10.1063/5.0073629, Nov. 16, 2021. The subject matter of this document was made by or originated from one or more members of the inventive entity of this patent application entitled METHOD TO IMPROVE PERFORMANCES OF TUNNEL JUNCTIONS GROWN BY METAL ORGANIC CHEMICAL VAPOR DEPOSITION,, which application claims priority to U.S. Provisional Patent Application No. 63/154,262, filed Feb. 26, 2021, by David Hwang, Matthew S. Wong, and Shuji Nakamura, entitled METHOD TO IMPROVE PERFORMANCES OF TUNNEL JUNCTIONS GROWN BY MOCVD,. 27. VoL 25. No. 24 21 Nov. 2017 OPTICS EXPRESS 30598 High wall-plug efficiency blue III-nitride LEDs designed for low current density operation, by Kuritsky et. al.
Device and Method Embodiments
(58) The present invention can be embodied in many ways including, but not limited to, the following embodiments (referring also to
(59) 27. The method of any of the examples 21-24, wherein the device comprises a micro-light emitting diode, the method further comprising: dry etching a mesa comprising the first n-type layer, the second n-type layer, the p-type layer, the tunnel junction, and the active region, wherein a top surface of the mesa has a surface area A of 6060 micrometers squared or less; and performing a number n of the treatment sequences such that a peak external quantum efficiency and a peak wall plug efficiency of the microled are both greater than 50% and the wall plug efficiency and the external quantum efficiency are both greater than 30% for the current density up to 30 Amps per centimeter square. 28. The method of any of the examples 21-27, wherein the microled is a blue microled emitting the electromagnetic radiation having a peak intensity at a blue wavelength. 29. The method of any of the example 28, further comprising performing the number n of treatment sequences wherein the light output power, external quantum efficiency, and wall plug efficiency are higher as compared to an equivalent microled without the tunnel junction and second n-type layer but further including an indium tin oxide p-contact layer on the p-type layer. 30. The method of any of the examples 21-27, wherein the microled is a green microled emitting the electromagnetic radiation having a peak intensity at a green wavelength. 31. The method of example 30, wherein the green microled has a light output power of at least 0.005 mW at a current density of 100 Amps per centimeter square. 32. The method of any of the examples 21-31, wherein the microled has a higher light output power, external quantum efficiency, and wall plug efficiency, and lower voltage, as compared to an equivalent led activated by thermal annealing through holes in mask on top of the mesa but without the sequence of treatments. 33. The method of any of the examples 21-32, further comprising selecting a thermal annealing temperature for activation that reduces the voltage between the anode contact layer and the cathode contact layer for the number of treatment sequences. 34. The method of example 33, wherein the annealing temperature is between 750 degrees Celsius and 800 degrees Celsius. 35. A device manufactured using the method of any of the examples 1-34. 36. A device 2200, 504 comprising: an activated p-type layer 2202, 502 comprising a III-Nitride based Mg-doped layer grown by vapor phase deposition or a growth method different from MBE (e.g., that incorporates hydrogen), wherein the p-type layer is activated through a sidewall 2250, 512 of the p-type layer after the removal of defects from the sidewall so as to increase a hole concentration of/in the p-type layer as compared to without the removal of the defects. 37. The device of example 36, further comprising: an active region 2208, 518 between a first n-type layer 2210 and the p-type layer; a second n-type layer 2204 on the p-type layer; and a tunnel junction 2206 between the second n-type layer and the p-type layer. 38. The device of example 37, wherein the activated p-type layer has a hole concentration characterized by a current density of at least 100 Amps per centimeter square flowing between the first n-type layer and the second n-type layer in response to a voltage of 4 volts or less applied across the first n-type layer and the second n-type layer. 39. The device of example 37 or 38, further comprising a light emitting device and a mesa 2252 comprising first the n-type layer, the second n-type layer, the p-type layer, and the active region, wherein the mesa has a light emitting top surface 2254 having an area A of 60 micron squared or less. 40. The device of example 39, wherein the area is 5 micron squared or less. 41. The device of any of the examples 38-40, wherein the current density is at least 300 amps per centimeter square. 42. The device of any of the examples 36-41, wherein the activated p-type layer has a hole concentration characterized by the device having a wall plug efficiency of at least 25%. 43. The device of any of the examples 36-42, wherein the device comprises a light emitting diode (e.g., micro LED), a laser, a solar cell, or a photodetector. 44. The device of example 43, comprising a transistor. 45. The device of example 43, comprising an electronic or optoelectronic device. 46. The device of any of the examples 36-45 manufactured by the method of any of the examples 1-35. 47. In III-nitride based devices or epitaxial layers, a III-nitride based Mg-doped layer is activated to increase the hole concentration through the sidewall of Mg-doped layer after removing at least a surface of the sidewall of Mg-doped layer. 48. After forming the mesa of III-nitride devices or epitaxial layers, the III-nitride based Mg-doped layer is activated to increase the hole concentration through the sidewall of Mg-doped layer of the mesa after removing at least surface of the sidewall of Mg-doped layer. 49. In any of the examples 47-48, the III-nitride based devices or epitaxial layers include a tunnel junction, wherein Mg-doped layer is covered at least at some region by n-type layer. 50. In any of the examples 47-49, for the activation, thermal annealing is used at temperatures more than 300 C. under the ambient gas which at least include air, O.sub.2 or oxide compound or diatomic gases. 51. In any of the examples 47-50, chemical etching is used to remove at least surface of the sidewall of Mg-doped layer. 52. In the example 51, the sidewall etching depth is more than 5 nm. 53. In the examples 51-52, the wet etchant contains oxygen or hydrogen atoms, includes KOH, H.sub.3PO.sub.4, HCl, etc. 54. In any of the examples 47-53, the device is an optical device such as a light-emitting diode (LED), laser diode, solar cell, or other device. 55. In any of the examples 47-54, wherein the device is an electronic device such as a transistor, High Electron Mobility Transistor (HEMT), a power device, etc. 56. The device or method of any of the examples 1-55, wherein the activation comprises removal of hydrogen from the p-type layer. 57. The device or method of any of the examples 1-56, wherein the p-type layer is characterized by having been grown by MOCVD and activation through the sidewall. 58. The device or method of any of the examples 1-57, wherein charge carriers tunnel across the tunnel junction via quantum mechanical tunneling. 59.
Advantages and Improvements
(60) A TJ is commercially useful for LED and laser applications because the TJ serves as the current spreading layer. Compared to other conventional current spreading layers, including semi-transparent metal layers, such as Ni/Au, or transparent and conductive oxides (TCOs), such as indium-tin oxide (ITO), the TJ is more optically transparent or less absorbing, which allows more light emitted from the device and enhances the light extraction efficiency of LEDs and lasers. A TJ grown by MOCVD is attractive, because MOCVD has been used widely in industry for III-nitride materials. The main drawback for the TJ grown by MOCVD is the voltage penalty due to insufficient hydrogen activation in the p-type layer, which increases the operating voltage and reduces the electrical efficiency. This invention provides a method to activate the p-type layer effectively from the sidewall using traditional cleanroom fabrication techniques.
(61) Nomenclature
(62) GaN and its ternary and quaternary compounds incorporating aluminum (Al) and indium (In) (AlGaN, InGaN, AlInGaN) are commonly referred to using the terms (Al,Ga,In)N, III-nitride, III-N, Group III-nitride, nitride, Group III-N, Al.sub.(1-x-y)InyGaxN where 0<x<1 and 0<y<1, or AlInGaN, as used herein. In addition, Scandium and Yttrium and other transition metal nitrides exist and alloys between transition metal nitrides and (Al,Ga,In)N can be formed (Al, Ga, In, Sc, Y)N. Boron nitride is another nitride which can form an alloy with (Al,Ga,In)N or (Al, Ga, In, Sc, Y)N. All these terms are intended to be equivalent and broadly construed to include respective nitrides of the single species, Al, Ga, and In, as well as binary, ternary and quaternary compositions of such Group III metal species. Accordingly, these terms comprehend the compounds AlN, GaN, and InN, as well as the ternary compounds AlGaN, GaInN, and AlInN, and the quaternary compound AlGaInN, as species included in such nomenclature. When two or more of the (Ga, Al, In) component species are present, all possible compositions, including stoichiometric proportions as well as off-stoichiometric proportions (with respect to the relative mole fractions present of each of the (Ga, Al, In) component species that are present in the composition), can be employed within the broad scope of the invention. Accordingly, it will be appreciated that the discussion of the invention hereinafter in primary reference to GaN materials is applicable to the formation of various other (Al, Ga, In)N material species. Further, (Al,Ga,In)N materials within the scope of the invention may further include minor quantities of dopants and/or other impurity or inclusional materials. Boron (B) may also be included.
(63) Group III-V material comprises an alloy of group III and group V elements in the periodic table.
(64) One approach to eliminating the spontaneous and piezoelectric polarization effects in GaN or III-nitride based optoelectronic devices is to grow the III-nitride devices on nonpolar planes of the crystal. Such planes contain equal numbers of Ga (or group III atoms) and N atoms and are charge-neutral. Furthermore, subsequent nonpolar layers are equivalent to one another so the bulk crystal will not be polarized along the growth direction. Two such families of symmetry-equivalent nonpolar planes in GaN are the {11-20} family, known collectively as a-planes, and the {1-100} family, known collectively as m-planes. Thus, nonpolar III-nitride is grown along a direction perpendicular to the (0001) c-axis of the III-nitride crystal.
(65) Another approach to reducing polarization effects in (Ga,Al,In,B)N devices is to grow the devices on semi-polar planes of the crystal. The term semi-polar plane (also referred to as semipolar plane) can be used to refer to any plane that cannot be classified as c-plane, a-plane, or m-plane. In crystallographic terms, a semi-polar plane may include any plane that has at least two nonzero h, i, or k Miller indices and a nonzero 1 Miller index.
(66) Some commonly observed examples of semi-polar planes include the (11-22), (10-11), and (10-13) planes. Other examples of semi-polar planes in the wurtzite crystal structure include, but are not limited to, (10-12), (20-21), and (10-14). The nitride crystal's polarization vector lies neither within such planes or normal to such planes, but rather lies at some angle inclined relative to the plane's surface normal. For example, the (10-11) and (10-13) planes are at 62.98 and 32.06 to the c-plane, respectively.
CONCLUSION
(67) This concludes the description of the preferred embodiment of the present invention. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.