CN115050866B - Polarization-controllable quantum dot Micro-LED homoepitaxial structure and preparation method thereof - Google Patents
Polarization-controllable quantum dot Micro-LED homoepitaxial structure and preparation method thereof Download PDFInfo
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Abstract
The application discloses a quantum dot Micro-LED homoepitaxial structure with controllable polarization and a preparation method thereof. The homoepitaxial structure includes: a semiconductor layer of a first conductivity type; the quantum well active region is grown on the semiconductor layer of the first conduction type and comprises a well region and a barrier region which are alternated, the well region is provided with a first superlattice structure and comprises a first GaN layer and an InN layer, and the barrier region is provided with a second superlattice structure and comprises an AlN layer and a second GaN layer; and a semiconductor layer of a second conductivity type grown on the quantum well active region. The homoepitaxial structure provided by the invention can reduce the energy band inclination of the quantum well active region, so as to reduce the polarization effect, increase the spatial overlap of electron and hole wave functions, improve the radiation probability and finally improve the internal quantum efficiency of the Micro-LED under the Micro size; the formed semiconductor material has high crystal quality, simple energy band regulation and control and easy quantum effect promotion, and is suitable for industrial production.
Description
Technical Field
The application relates to an LED epitaxial structure, in particular to a quantum dot Micro-LED homoepitaxial structure with controllable polarization and a preparation method thereof, and belongs to the technical field of semiconductors.
Background
Micro-LED is the current research focus, and it is as the optoelectronic device of new generation, obtains extensive attention and application in fields such as novel demonstration, optical communication and optical detection.
Due to the difficulty in obtaining nonpolar GaN materials, the current commercial products are based on GaN grown on the C-plane, which is a polar plane, and a spontaneous polarization electric field exists, and meanwhile, the lattice mismatch between the InGaN active region and GaN active region causes a piezoelectric polarization electric field.
Due to the existence of the polarized electric field, the spatial overlapping of electron and hole wave functions is reduced, the radiative recombination probability is reduced, and the quantum efficiency in the micro-LED is reduced. And because the micro-LED has higher requirement on wavelength uniformity and more drastic current change, the peak wavelength under the original polarization field effect can shift, so that the phenomenon of display chromatic aberration is more serious.
The traditional LED structure can not meet the requirements of the Micro-LED in the aspects of crystal quality, efficiency reduction caused by polarization effect control and the like. Even though some prior arts propose to use AlInN material as barrier layer material to realize the regulation of polarization, it is difficult to realize industrial commercialization because the AlInN material has extremely difficult growth and poor material quality.
Disclosure of Invention
The application mainly aims to provide a quantum dot Micro-LED homoepitaxial structure with controllable polarization and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the above purpose, the present application adopts a technical solution comprising:
in a first aspect, the present invention provides a polarization-controllable quantum dot Micro-LED homoepitaxial structure, including:
a semiconductor layer of a first conductivity type grown on the nitride single crystal substrate;
a quantum well active region grown on the semiconductor layer of the first conductivity type and including one or more well regions and one or more barrier regions alternately grown, the quantum well active region having one or more cyclic growth periods;
the well region is provided with a first superlattice structure, the first superlattice structure is provided with more than one second growth period, each period of the first superlattice structure comprises an InN layer and a first GaN layer which are sequentially grown, and the first superlattice structure enables an epitaxial structure grown in the well region to be subjected to tensile stress; the barrier region is provided with a second superlattice structure, the second superlattice structure is provided with more than one third growth period, each period of the second superlattice structure comprises an AlN layer and a second GaN layer which are sequentially grown, and the second superlattice structure enables the epitaxial structure after the growth of the barrier region to be subjected to compressive stress;
a semiconductor layer of a second conductivity type grown on the quantum well active region.
Further, the value of the cycle growth period of the well region and the barrier region is 1-20.
Further, the thicknesses of the plurality of first GaN layers are the same in the first superlattice cycle period.
Further, the thicknesses of the plurality of InN layers are the same in the first superlattice cycle period.
Further, the thicknesses of the plurality of second GaN layers are the same in the second superlattice cycle period.
Further, the plurality of AlN layers have the same thickness during the second superlattice cycle.
Further, in the cyclic growth cycle, the thickness of the first GaN layer grown firstly is greater than or equal to that of the first GaN layer grown last, and the thickness of the InN layer grown firstly is smaller than that of the InN layer grown last; and/or in the cyclic growth cycle, the thickness of the AlN layer growing firstly is less than that of the AlN layer growing last, and the thickness of the second GaN layer growing firstly is more than or equal to that of the second GaN layer growing last; wherein the emission wavelength of the quantum well active region is >600nm.
Further, the emission wavelength of the quantum well active region is >600nm.
Further, the first superlattice cycle period of the first superlattice structure has a value of 1-10.
Further, the thickness of the first GaN layer is 0.2-1.0nm.
Further, the thickness of the InN layer is 0.1-0.5nm.
Further, the second superlattice cycle period of the second superlattice structure has a value of 1-20.
Further, the AlN layer has a thickness of 0.5 to 1.5nm.
Further, the thickness of the second GaN layer is 1.0-5.0nm.
Further, the InN layer comprises a plurality of InN quantum dots, and the particle height of the InN quantum dots is 0.1-0.5nm.
In a second aspect, the invention also provides a preparation method of the polarization-controllable quantum dot Micro-LED homoepitaxial structure, which comprises the steps of growing a semiconductor layer of a first conduction type, a quantum well active region and a semiconductor layer of a second conduction type on a nitride single crystal substrate in sequence; the step of growing the quantum well active region specifically comprises:
s1, growing to form a well region under the conditions of a first temperature and a first pressure, wherein the well region is provided with a first superlattice structure, and each period of the first superlattice structure comprises a first GaN layer and an InN layer which are grown in sequence.
And S2, growing to form a barrier region under the conditions of a second temperature and a second pressure, wherein the barrier region is provided with a second superlattice structure, and each period of the second superlattice structure comprises an AlN layer and a second GaN layer which grow in sequence.
The second temperature is above a first temperature and the first pressure condition is above a second pressure condition.
Further wherein the step of growing the quantum well active region further comprises:
and S3, repeating the operations of the steps S1-S2 more than once to alternately grow a plurality of well regions and a plurality of barrier regions.
Further, the first pressure is 200-500torr, the first temperature is 600-800 ℃, the second pressure is 50-200torr, and the second temperature is 800-1000 ℃.
Further, the number of cycles of the first superlattice structure is 1-10, and/or the thickness of the first GaN layer is 0.2-1.0nm, and/or the thickness of the InN layer is 0.1-0.5nm.
Further, the number of cycles of the second superlattice structure is 1-20, and/or the AlN layer has a thickness of 0.5-1.5nm, and/or the second GaN layer has a thickness of 1.0-5.0nm.
Further, step S1 specifically includes: and simultaneously or alternatively inputting an In source and a nitrogen source into the growth chamber, thereby growing and forming the InN layer.
Compared with the prior art, the beneficial effects of the technical scheme of the application at least comprise:
the design of a quantum well active region of the quantum dot Micro-LED homoepitaxial structure with controllable polarization is different from that of an InGaN/GaN active region quantum well structure in a traditional heteroepitaxial structure, and based on a quantum energy band regulation type well region and a barrier region of GaN single crystal substrate growth cycle, the well region in each cycle is composed of InN/GaN superlattice with cycle, and the barrier region in each cycle is composed of AlN/GaN superlattice with cycle, so that the energy band inclination of the quantum well active region can be reduced, the polarization effect is reduced, the overlapping of electron and hole wave functions on space is increased, the radiation probability is improved, and the internal quantum efficiency of the Micro-LED under a tiny size is finally improved.
Meanwhile, the preparation method provided by the invention can regulate and control the stress of the semiconductor layer through the mutual matching of the compressive stress and the tensile stress, and the formed semiconductor material has high crystal quality, simple energy band regulation and control and easy quantum effect promotion, and is suitable for industrial production.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present invention and to implement the technical means according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic diagram illustrating the influence of the polarized field effect on the bandgap structure in the epitaxial structure of the LED in the prior art.
Fig. 2 is a schematic structural diagram of a polarization-controllable quantum dot Micro-LED homoepitaxial structure according to an exemplary embodiment of the present invention.
Fig. 3a is a quantum dot morphology schematic diagram of a quantum dot Micro-LED homoepitaxial structure with controllable polarization according to an exemplary embodiment of the present invention.
Fig. 3b is a schematic diagram of the band polarization state of the homoepitaxial structure of the polarization-controllable quantum dot Micro-LED provided by an exemplary embodiment of the present invention.
Fig. 3c is a schematic diagram of a stress distribution state of a homo-epitaxial structure of a polarization-controllable quantum dot Micro-LED according to an exemplary embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be further noted that, for the convenience of description, only some of the structures related to the present application are shown in the drawings, not all of the structures. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
As shown in fig. 1, the active region quantum well InGaN/GaN structure of the conventional epitaxial structure in the prior art has a strong polarization field, space charges are formed at the interface, and the conduction band and the valence band are tilted, resulting in a reduction in the overlap of the electron and hole wave functions. Therefore, in order to overcome the defects in the prior art, the inventor of the invention has been put forward the technical scheme of the invention through long-term practice.
The embodiment of the invention provides a polarization-controllable quantum dot Micro-LED homoepitaxial structure, which comprises: a semiconductor layer of a first conductivity type grown on the nitride single crystal substrate; a quantum well active region grown on the semiconductor layer of the first conductivity type and including one or more well regions and one or more barrier regions alternately grown, the quantum well active region having one or more cyclic growth periods N; the well region is provided with a first superlattice structure, the first superlattice structure is provided with more than one second growth period x, each period of the first superlattice structure comprises an InN layer and a first GaN layer which grow in sequence, and the first superlattice structure enables an epitaxial structure grown in the well region to be under tensile stress; the barrier region is provided with a second superlattice structure, the second superlattice structure is provided with more than one third growth period y, each period of the second superlattice structure comprises an AlN layer and a second GaN layer which are sequentially grown, and the second superlattice structure enables the epitaxial structure after the growth of the barrier region to be subjected to compressive stress; a semiconductor layer of a second conductivity type grown on the quantum well active region.
Meanwhile, the embodiment of the invention also provides a preparation method of the polarization-controllable quantum dot Micro-LED homoepitaxial structure, which comprises the following steps:
a semiconductor layer of a first conductivity type, a quantum well active region, and a semiconductor layer of a second conductivity type are grown in this order on a nitride single crystal substrate.
The step of growing the quantum well active region specifically comprises the following substeps:
s1, growing to form a well region under the conditions of a first temperature and a first pressure, wherein the well region is provided with a first superlattice structure, and each period of the first superlattice structure comprises a first GaN layer and an InN layer which are grown in sequence.
And S2, growing to form a barrier region under the conditions of a second temperature and a second pressure, wherein the barrier region is provided with a second superlattice structure, and each period of the second superlattice structure comprises an AlN layer and a second GaN layer which grow in sequence.
The second temperature is above a first temperature and the first pressure condition is above a second pressure condition.
In some embodiments, the method may further include: and S3, repeating the operations of the steps S1-S2 more than once to alternately grow a plurality of well regions and a plurality of barrier regions.
As a typical example of the above technical solution, as shown in fig. 2, the polarization-controllable quantum dot Micro-LED homoepitaxial structure provided in the embodiment of the present invention grows N-type and P-type GaN regions on an N-type GaN single crystal substrate, where a quantum well active region is a quantum energy band control structure, specifically N cycles, and each cycle includes a well region and a barrier region of a superlattice structure. The semiconductor layer of the well region is made of InN and GaN in sequence, the thicknesses of the InN and the GaN are a and b respectively, and the number of cycles is x; the materials of the semiconductor layer of the barrier region are AlN and GaN in sequence, the thicknesses of the semiconductor layer are c and d respectively, and the number of cycles is y. The thickness of each structural layer corresponding to each cycle is from a 1 ，b 1 ，c 1 ，d 1 To a 2 ，b 2 ，c 2 ，d 2 To a n ，b n ，c n ，d n The thickness of the respective semiconductor layers may be the same or different for each cycle period. Whether the parameters are the same or not and the variation degree are determined by the quantum dots, the energy bands and polarization regulation.
Based on the technical scheme, the embodiment of the invention provides a Micro-LED homoepitaxial structure with quantum energy band regulation, the innovation of the structure is that the active region is designed, and the structure is different from an active region quantum well structure of InGaN/GaN in a traditional heteroepitaxial structure.
The invention can realize different growth modes of the quantum dots by adjusting the thicknesses a and b of InN/GaN superlattice of the well region, as shown in figure 3 a. The choice of InN rather than InGaN serves to maximize the local effect of In, improving the luminous efficiency. InGaN grows in a continuous thin film state, and InN is in a quantum dot state. The thickness a of InN determines the energy band height of the formed well region, further determines the light-emitting wavelength, and controls the growth form of quantum dots, and the pitch and density of the quantum dots. The thickness b of GaN is determined by a, and plays a role In covering and protecting InN, for example, the density of a/b × quantum dot InN (the density is generally controlled by growth pressure and temperature, and is a fixed value) obtains the actual In content, that is, can be used for indicating the target wavelength, so the thickness b can be reversely deduced by the design wavelength, and finally a well region with the designed InN concentration and better quality is formed, and simultaneously the adjustment of the energy band shape of the final well region is played, and the adjustment of the energy band shape is shown as a dotted line corresponding to the well region part In fig. 3 b.
Similarly, the thicknesses c and d of the AlN/GaN superlattice of the barrier region are matched, so that on one hand, the height of a potential barrier can be adjusted through the AlN thickness c to play a role in quantum confinement of a well region, on the other hand, the energy band can be adjusted, for example, the energy band can be processed by being similar to AlGaN in energy band calculation, and the content of Al components is obtained through the value of c/d to obtain the corresponding energy band width, so that the energy band is adjusted; as shown by the dotted line corresponding to the barrier region in fig. 3b, the dynamic matching with zero polarization of GaN is finally realized by the well region, so that the non-overlapping of the wave functions between electron holes caused by the polarization effect in the conventional structure is eliminated.
In addition, the quantum dot Micro-LED homoepitaxial structure provided by the embodiment of the invention can also adjust the stress of the epitaxial layer, and is specifically represented as follows: due to the large lattice constant of InN, the epitaxial layer will generate large tensile stress after the well region grows, and then the epitaxial layer enters the growth of the barrier region. The material of the barrier region is AlN/GaN superlattice, and compressive stress can be introduced into the epitaxial layer to offset tensile stress of the well region. By the alternate growth of the two layers of superlattice, the stress can be regulated while the crystal quality is ensured, and the stress regulation state in one growth cycle is shown in fig. 3 c.
The energy band polarization diagram of the epitaxial structure provided by the embodiment of the invention corresponds to the stress control diagram. As shown in fig. 3b, due to the alternation of tensile stress and compressive stress, the energy band shapes of the well region and the barrier region are adjusted, and the tilt of the energy band is reduced or avoided, compared with fig. 1 in the prior art, after the energy band adjustment, the phenomenon of non-overlapping of electron and hole wave functions can be reduced or eliminated, thereby improving the radiative recombination probability.
The thickness values a, b, c and d of each layer in each cycle in the epitaxial structure are not necessarily consistent, and the matching of different quantum dot forms, energy band polarization and stress control can be realized, so that the light-emitting wavelength and high-quality light-emitting well regions of different quantum wells in the same structure and flexible design under different working conditions are realized. The specific method of adjusting the matching may be exemplified as follows, but is not limited to the specific exemplary manner described below.
In more specific embodiments, the embodiments of the present invention can be further exemplified by combining the above preparation method of the polarization-controllable quantum dot Micro-LED homoepitaxial structure with the structure composition thereof:
the embodiment of the invention is based on a GaN single crystal substrate, and the N-type GaN region is grown on the GaN single crystal substrate and then enters the quantum energy band regulation active region. Growing in the well region at 600-800 deg.C under 200-500torr pressure, growing GaN layer with thickness b 1 0.2-1.0nm, followed by growing an InN layer, in two ways, one is conventionally introducing TMIn and NH at the same time 3 The other is TMIn and NH 3 Alternately introducing to control the thickness a of the InN layer 1 The thickness of the material layer (namely the height of InN quantum dot particles) is 0.1-0.5nm, the number x of superlattice periods is 1-10, and finally the GaN layer is used for ending, the pressure is used for controlling the size of InN quantum dots, and the temperature is used for controlling the distribution spacing and density of the InN quantum dots. The general rule is that when the pressure is increased, the size of InN quantum dots becomes larger, and the size is preferably controlled within the range of 10-100 nm; and the higher the temperature is, the smaller the spacing of InN quantum dots becomes, and the spacing is preferably controlled within the range of 0.1-1 um.
Then the substrate enters a barrier region for growth, the pressure is reduced to 50-200torr, the growth temperature is 800-1000 ℃, and the energy band is calculated according to the InN/GaN ratio of the well region to obtain the matched AlN/GaN growth thicknessDegree and period. Growing AlN material to a thickness c 1 0.5-1.5nm, followed by growth of GaN material to a thickness d 1 1.0-5.0nm, and 1-20 superlattice periods y. In the step, the compactness and continuity of the AlN layer are ensured by controlling the lower pressure and the higher temperature compared with the well region growth so as to form better quantum energy band matching. In a preferred embodiment of the present invention, the selection of the above parameters is closely related, and the values of c and d are determined by the values of a and b, and the inventor finds that a suitable empirical relationship is: (c + d). Times.y: (a + b) x =5 to 10,2 to 3 xd/c = a/b, and the quantum energy band calculated based on the formula can be matched with the quantum energy band to always obtain better energy band and polarization control effect.
In general, the thicknesses of the layers in the well region and the barrier region in each cyclic growth period are preferably constant, which can reduce the complexity of the process and is beneficial to the stability of the process. But in the preparation of epitaxial structures of particularly long emission wavelengths (e.g. dominant wavelength)>600 nm), since the polarization effect is more serious than usual, the well region thickness a is set at this time n >a 1 ，b n ≤b 1 Barrier zone thickness c n >c 1 ，d n ≤d 1 The setting of (n =2,3, … …) is more suitable. It can be understood that, for the case where the polarization effect is severe due to the long dominant wavelength, the stress control is increased by gradually increasing the thickness of InN and gradually increasing the thickness of AlN in the cyclic growth period, so as to reduce or avoid a larger energy band tilt; more specifically, the variation trend of the well InN thickening, gaN thinning, the base AlN thickening and GaN thinning may be set, preferably, the variation rate of each layer in each cycle growth period should be set to 4% to 12%, most preferably, the variation rate of the well thickness parameter a is about 10%, for example, 8% to 12%, the variation rate of the base thickness value c is about 5%, for example, 4% to 6%, b and d may be unchanged, or may preferably be reduced by an equivalent proportion of b to a or d to c, so as to generate the optimal polarization control for the epitaxial structure with longer light emitting wave.
The number of cycles N of the whole quantum energy band regulation active region is 1-20 and is not equal no matter whether the thicknesses in the well region and the barrier region of each cycle are changed or not and how the thicknesses are changed.
The technical solutions of the present invention are further illustrated by the following several more specific examples, however, it should be understood that the following examples are only some of the preferred and representative examples of the numerous embodiments of the present invention, and the following examples should not be construed as all examples of the present invention, i.e., the following examples should not be construed as limiting the scope of the present invention.
Example 1:
this example illustrates a preparation process of a quantum dot Micro-LED homoepitaxial structure with controllable polarization, which is specifically as follows:
(1) An N-type gallium nitride layer with a thickness of 0.5 μm and a doping concentration of Si of 8X 10 was grown on a nitride single crystal substrate at a temperature of 1060 ℃ and a growth pressure of 200torr 18 cm -3 The Ga source required by the growth is TMG source, and the growth atmosphere is H 2 An atmosphere.
(2) And growing the quantum well active region, including steps S1-S3.
S1: firstly introducing TMGa source and NH under the conditions of 400torr and 700 DEG C 3 Growing a GaN layer with the thickness of 0.7nm for priming, and then introducing TMIn and NH 3 Growing an InN layer to a thickness a 1 At 0.1nm, introducing TMGa source and NH 3 Growing a GaN layer with a thickness b 1 At 0.7nm and a period x of 3 cycles, the well region growth is completed.
S2: then, an AlN layer having a thickness c of 100torr and 900 ℃ is grown 1 0.5nm, regrown GaN layer of thickness d 1 The growth of barrier regions was completed with a period of 3.5nm and a period of 3 cycles y.
S3: and repeating the growth steps of the well region and the barrier region, and circularly growing for 10 periods.
(3) Growing a 150nm p-type gallium nitride layer at 930 deg.C and 200torr growth pressure with Mg doping concentration of 5 × 10 19 cm -3 The Ga source required for growth is TMG source, and the Mg source is Cp 2 Mg in growth atmosphere of H 2 An atmosphere.
Comparative example 1-1:
this comparative example belongs to a typical growth example in the prior art, and is substantially the same as example 1, except mainly for the difference in growth of the quantum well active region in step (2):
s1: TMIn, TMGa and NH are simultaneously introduced at 200torr and 750 DEG C 3 And growing the InGaN well layer material by 2.5nm.
S2: and growing a GaN barrier layer with the thickness of 12.5nm at the temperature of 850 ℃ and at the temperature of 200 torr.
S3: the above step of the well barrier cycle growth is repeated for 10 cycles.
The epitaxial structure connection electrodes provided by the embodiment 1 and the comparative example 1 are prepared into light-emitting devices, the structures of other structures of the corresponding devices of the embodiment 1 and the comparative example 1, including the N-type GaN layer, the P-type GaN layer and the connection electrodes are completely consistent, a light-emitting test is carried out, and the following result is obtained through the test, wherein the wavelength deviation is 1-1000A/cm 2 Wavelength shift at current density.
Table 1 test of emission properties of light emitting devices obtained in example 1 and comparative examples 1 to 1
As can be seen from the above test results, in example 1 using the technical scheme of the present invention, because polarization is controllable and technical design is possible, the obtained dominant wavelength is basically the same as that obtained by the conventional method, and the emission intensity and the quantum efficiency are improved to different degrees, indicating that the overlap of the wave functions of electrons and holes in the quantum well is increased, and radiative recombination is enhanced. Finally, under the condition of increasing current density, the offset of the embodiment 1 is almost only half of the blue shift offset of the comparison example 1, which shows that the polarization effect is well regulated and controlled by the invention, and the Quantum Confined Stark Effect (QCSE) is reduced.
Comparative examples 1 to 2:
this comparative example belongs to a typical growth example in the prior art, and is substantially the same as example 1, except mainly for the difference in growth of the quantum well active region in step (2):
replacing InN grown in the step S1 with the introduced TMIn, TMG and NH 3 InGaN is grown to replace InN, and the rest conditions and the thicknesses of all layers are unchanged.
The light emitting device formed had a light emission intensity of 90%, which was slightly lower than that of example 1.
Comparative examples 1 to 3:
this comparative example belongs to a typical growth example in the prior art, and is substantially the same as example 1, except mainly for the difference in growth of the quantum well active region in step (2):
in step S1, when the InN layer is formed, the excess pressure is 600torr, the temperature is 900 ℃, and the rest conditions and the thickness of each layer are unchanged.
The formed light emitting device can not emit light in the visible light range, which is caused by the fact that the particle size and distribution density of InN quantum dots do not meet the visible light emission requirement.
Example 2:
this example illustrates a preparation process of a quantum dot Micro-LED homoepitaxial structure with controllable polarization, which is substantially the same as that of example 1, and differs mainly in the formation process of the quantum well active region:
s1: TMIn and NH are simultaneously introduced under the conditions of 200torr and 800 DEG C 3 Growing an InN layer to a thickness a 1 0.3nm, and growing a GaN layer with a thickness b by the same GaN growth process 1 The period x is 1 at 0.2nm, and the well region growth is completed.
S2: then, an AlN layer having a thickness c is grown at 1000 ℃ under a condition of 50torr 1 1.5nm, regrown GaN layer of thickness d 1 The barrier region growth was completed with a cycle number y of 2 at 1.0nm.
S3: and repeating the growth steps of the well region and the barrier region, and circularly growing for 20 periods.
The homoepitaxial structure prepared by the embodiment is 1-1000A/cm 2 The current density was measured with the same level of wavelength shift as in example 1.
Example 3
This example illustrates a preparation process of a quantum dot Micro-LED homoepitaxial structure with controllable polarization, which is substantially the same as that of example 1, and differs mainly in the formation process of the quantum well active region:
s1: TMIn and NH are simultaneously introduced under the conditions of 500torr and 600 DEG C 3 Growing an InN layer to a thickness a 1 0.2nm, and growing a GaN layer with a thickness b 1 At 1.0nm and a cycle number x of 10, the well region growth is completed.
S2: then, an AlN layer having a thickness c is grown at 800 ℃ at 200torr 1 0.9nm, regrown GaN layer of thickness d 1 The growth of the barrier region is completed with a period y of 20 at 5.0nm.
S3: the growth steps of the well region and the barrier region are not repeated, and the cyclic growth is carried out for 1 period in total.
The homoepitaxial structure prepared by the embodiment is 1-1000A/cm 2 The wavelength shift amount was the same as that in example 1 even at the current density.
Example 4
This example illustrates a process for preparing a polarization-controllable quantum dot Micro-LED homoepitaxial structure, which is substantially the same as that in example 1, except for the difference in the formation process of the quantum well active region:
s1: TMIn with the flow rate of 1000sccm and NH with the flow rate of 70slm are simultaneously introduced at 580 ℃ under the condition of 500torr 3 Growing an InN layer to a thickness a 1 0.4nm, and growing a GaN layer with a thickness b by conventional GaN growth process 1 At 1.0nm and a cycle number x of 10, the well region growth is completed. Wherein the growth process is controlled so that the emission wavelength is 650nm.
S2: then, an AlN layer having a thickness c of 200torr and 760 ℃ is grown 1 1.5nm, regrown GaN layer of thickness d 1 The growth of barrier regions was completed with a period of 20 cycles y of 5.0nm.
S3: the growth steps of the well region and the barrier region are not repeated, and the cyclic growth is carried out for 2 periods in total. And, the thickness of the above a is increased by 10%, the thickness of c is increased by 5%, and the thicknesses of b and d are not changed every cycle.
Comparative example 2
This example illustrates a preparation process of a quantum dot Micro-LED homoepitaxial structure with controllable polarization, which is substantially the same as that of example 4, and the differences are mainly as follows:
in step S3, in each period, the parameters a, b, c, d are consistent with the first period and are not changed.
Table 2 test of emission properties of light emitting devices obtained in example 1 and comparative examples 1 to 1
In comparative examples 1 to 3, since visible light was not generated, the parameters such as dominant wavelength, emission intensity, quantum efficiency, and wavelength shift were not measured.
Comparing example 4 with comparative example 2 at 1-1000A/cm 2 The wavelength shift amount at current density was 48nm for example 4 and 70nm for comparative example 2, which were significantly larger than those of example 4. It can be found that for an epitaxial structure with a longer wavelength, especially a main light-emitting wavelength longer than 600nm, it is preferable to use a method of performing variable control on the thickness parameter in different periods to perform growth, so as to obtain a higher light-emitting intensity and a lower wavelength offset, so as to generate a smaller chromatic aberration.
Through the embodiments and the proportion, it is clear that the quantum dot Micro-LED homoepitaxial structure with controllable polarization provided by the embodiments of the present invention is different from an InGaN/GaN active region quantum well structure in a traditional heteroepitaxial structure in the design of a quantum well active region, and based on a quantum energy band regulation and control type well region and a barrier region of a GaN single crystal substrate growth cycle, the well region in each cycle is composed of a periodically circulating InN/GaN superlattice, and the barrier region in each cycle is composed of a periodically circulating AlN/GaN superlattice, so that the energy band tilt of the quantum well active region can be reduced, the polarization effect can be reduced, the spatial overlap of electron and hole wave functions can be increased, the radiation probability can be increased, and finally the internal quantum efficiency of the Micro-LED under a Micro size can be improved.
Meanwhile, the preparation method provided by the embodiment of the invention can also regulate and control the stress of the semiconductor layer through the mutual matching of the compressive stress and the tensile stress, and the formed semiconductor material has high crystal quality, simple energy band regulation and control and easy quantum effect promotion, and is suitable for industrial production.
The above description is only an embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the specification and the drawings of the present application, or which are directly or indirectly applied to other related technical fields, are also included in the scope of the present application.
Claims (10)
1. A polarization-controllable quantum dot Micro-LED homoepitaxial structure is characterized by comprising:
a semiconductor layer of a first conductivity type grown on the nitride single crystal substrate;
a quantum well active region grown on the semiconductor layer of the first conductivity type and including one or more well regions and one or more barrier regions alternately grown, the quantum well active region having one or more cyclic growth periods;
the well region is provided with a first superlattice structure, the first superlattice structure is provided with more than one first superlattice cycle period, each period of the first superlattice structure comprises an InN layer and a first GaN layer which are sequentially grown, and the first superlattice structure enables an epitaxial structure grown in the well region to be subjected to tensile stress; the barrier region is provided with a second superlattice structure, the second superlattice structure is provided with more than one second superlattice cycle period, each period of the second superlattice structure comprises an AlN layer and a second GaN layer which are sequentially grown, and the second superlattice structure enables the epitaxial structure grown in the barrier region to be subjected to compressive stress;
a semiconductor layer of a second conductivity type grown on the quantum well active region.
2. The polarization-controllable quantum dot Micro-LED homoepitaxial structure of claim 1, wherein: the value of the cycle growth period of the well region and the barrier region is 1-20.
3. The polarization-controllable quantum dot Micro-LED homoepitaxial structure of claim 1, wherein: in the first superlattice cycle period, the thicknesses of the plurality of first GaN layers are the same, and/or the thicknesses of the plurality of InN layers are the same;
and/or the thicknesses of the plurality of second GaN layers are the same, and/or the thicknesses of the plurality of AlN layers are the same in the second superlattice cycle period.
4. The polarization-controllable quantum dot Micro-LED homoepitaxial structure of claim 1, wherein: in the cyclic growth period, the thickness of the first GaN layer grown firstly is greater than or equal to that of the first GaN layer grown last, and the thickness of the InN layer grown firstly is smaller than that of the InN layer grown last;
and/or in the cyclic growth cycle, the thickness of the AlN layer growing firstly is less than that of the AlN layer growing last, and the thickness of the second GaN layer growing firstly is more than or equal to that of the second GaN layer growing last;
wherein the emission wavelength of the quantum well active region is >600nm.
5. The polarization-controllable quantum dot Micro-LED homoepitaxial structure of claim 1, wherein: the value of the first superlattice cycle period of the first superlattice structure is 1-10, and/or the thickness of the first GaN layer is 0.2-1.0nm, and/or the thickness of the InN layer is 0.1-0.5nm;
and/or the second superlattice cycle period of the second superlattice structure has a value of 1-20, and/or the AlN layer has a thickness of 0.5-1.5nm, and/or the second GaN layer has a thickness of 1.0-5.0nm.
6. The polarization-controllable quantum dot Micro-LED homoepitaxial structure of claim 5, wherein: the InN layer comprises a plurality of InN quantum dots, and the particle height of the InN quantum dots is 0.1-0.5nm.
7. A preparation method of a polarization-controllable quantum dot Micro-LED homoepitaxial structure comprises the steps of growing a semiconductor layer of a first conduction type, a quantum well active region and a semiconductor layer of a second conduction type on a nitride single crystal substrate in sequence;
the method is characterized in that the step of growing the quantum well active region specifically comprises the following steps:
s1, growing to form a well region under the conditions of a first temperature and a first pressure, wherein the well region is provided with a first superlattice structure, and each period of the first superlattice structure comprises a first GaN layer and an InN layer which are grown in sequence;
s2, growing and forming a barrier region under the conditions of a second temperature and a second pressure, wherein the barrier region has a second superlattice structure, and each period of the second superlattice structure comprises an AlN layer and a second GaN layer which are grown in sequence;
the second temperature is above a first temperature and the first pressure condition is above a second pressure condition.
8. The method for preparing a polarization-controllable quantum dot Micro-LED homoepitaxial structure according to claim 7, wherein the step of growing the quantum well active region further comprises:
and S3, repeating the operations of the steps S1-S2 more than once to alternately grow a plurality of well regions and a plurality of barrier regions.
9. The method for preparing a polarization-controllable quantum dot Micro-LED homoepitaxial structure according to any one of claims 7 to 8, wherein:
the first pressure condition is 200-500torr, the first temperature is 600-800 ℃, the second pressure condition is 50-200torr, and the second temperature is 800-1000 ℃;
and/or the number of cycles of the first superlattice structure is 1-10, and/or the thickness of the first GaN layer is 0.2-1.0nm, and/or the thickness of the InN layer is 0.1-0.5nm;
and/or the periodicity of the second superlattice structure is 1-20, and/or the AlN layer has a thickness of 0.5-1.5nm, and/or the second GaN layer has a thickness of 1.0-5.0nm.
10. The method for preparing a quantum dot Micro-LED homoepitaxial structure with controllable polarization according to any one of claims 7 to 8, wherein the step S1 specifically comprises: and simultaneously or alternatively inputting an In source and a nitrogen source into the growth chamber, thereby growing and forming the InN layer.
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