WO2014119910A1 - 나노구조 반도체 발광소자 제조방법 - Google Patents
나노구조 반도체 발광소자 제조방법 Download PDFInfo
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- WO2014119910A1 WO2014119910A1 PCT/KR2014/000811 KR2014000811W WO2014119910A1 WO 2014119910 A1 WO2014119910 A1 WO 2014119910A1 KR 2014000811 W KR2014000811 W KR 2014000811W WO 2014119910 A1 WO2014119910 A1 WO 2014119910A1
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Definitions
- the present invention relates to a method of manufacturing a nanostructured semiconductor light emitting device.
- a semiconductor light emitting device such as a light emitting diode (LED) is a device in which a substance contained in a device emits light. The electrons and holes are recombined to convert the generated energy into light and emit the light.
- LEDs are now widely used as lights, displays, and light sources, and their development is accelerating.
- a method of manufacturing a semiconductor device comprising: providing a base layer made of a first conductivity type semiconductor; forming a mask including an etch stop layer on the base layer; Forming a plurality of nanocores by growing a first conductivity type semiconductor in an exposed region of the base layer such that the plurality of openings are filled; The method comprising: partially removing the mask using the etch stop layer to expose the plurality of nanostructures; and sequentially growing an active layer and a second conductivity type semiconductor layer on the surface of the plurality of nanocores, And a manufacturing method thereof.
- the mask comprises a first material layer formed on the base layer and provided as the etch stop layer, a second material layer formed on the first material layer and having an etch rate lower than the etch rate of the first material layer, 2 < / RTI > material layer.
- the mask comprises first to third material layers sequentially formed on the base layer, the second material layer being made of a material different from the first and third material layers, Can be provided as a stop layer.
- the first and third material layers may be made of the same material.
- the etch stop level of the etch stop layer may be less than 1/3 of the total height of the mask from the surface of the base layer.
- the aspect ratio of the opening may be at least 5: 1.
- the step of forming a diffusion prevention film made of a material different from that of the mask on each of the inner sidewalls of the plurality of openings is provided between the step of forming the plurality of openings and the step of forming the plurality of nanocores .
- the forming of the diffusion barrier layer may include forming a material layer for the diffusion barrier layer on the surface of the mask, forming a diffusion barrier layer on the upper surface of the mask and the exposed region of the base layer, And removing the portion located in the second region.
- the method may further include removing the diffusion barrier layer from an exposed surface of the nanocore, prior to sequentially growing the active layer and the second conductive semiconductor layer.
- a portion of the diffusion barrier below the upper level of the etch stop layer may remain.
- the method may further include a step of partially removing the mask and a step of sequentially growing the active layer and the second conductivity type semiconductor layer, followed by heat treating the plurality of nanocores.
- the step of heat-treating the plurality of nanocores may be performed in a temperature range of 600 to 1,200 ° C.
- the method may further include applying a polishing process so that the upper surfaces of the plurality of nanocores are planarized to the same level.
- At least a part of the plurality of nanocores may be designed so that at least one of the cross-sectional area and the gap is different from the other nanocore.
- a semiconductor device comprising: a base layer made of a first conductive semiconductor; a mask formed on the base layer, the mask having a plurality of openings in which the base layer region is exposed; A plurality of nano-light-emitting structures each having a nanocore made of a first conductive semiconductor, an active layer sequentially formed on a surface of the nanocore, and a second conductive semiconductor layer; Diffusion preventing film.
- the mask structure as a mold, it is possible to stably grow a three-dimensional nanostructure having a high aspect ratio, and consequently, it is advantageous to increase the light emitting area.
- the polishing process can be easily applied, so that the uniform height of the final nanostructure can be assured.
- Such a process can be particularly useful when different cross sections and spacing of nanostructures are required to realize multi-wavelength light (e.g., white light).
- FIGS. 1 to 5 are cross-sectional views for explaining a method of fabricating a nano-structured semiconductor light emitting device according to an embodiment of the present invention.
- Figs. 6 and 7 are plan views of a mask showing the shape of an opening that can be formed in the mask employed in the present invention.
- Figs. 8 and 9 are side cross-sectional views showing the shapes of openings that can be formed in the mask employed in the present invention.
- FIGS. 10 to 14 are cross-sectional views showing major steps of an electrode forming process applicable to the nano-structured semiconductor light emitting device obtained in FIG.
- FIGS. 15 to 21 are cross-sectional views of major processes for explaining another example of the method of manufacturing a nano-structured semiconductor light emitting device of the present invention.
- FIGS. 22 and 23 are schematic diagrams for explaining a heat treatment process which can be applied to the processes of FIGS. 18 and 19.
- FIG. 22 and 23 are schematic diagrams for explaining a heat treatment process which can be applied to the processes of FIGS. 18 and 19.
- Figs. 24 to 27 are cross-sectional views of major processes for explaining an example of a process of forming electrodes for the result shown in Fig.
- FIGS. 28 to 31 are cross-sectional views for explaining a method of manufacturing a nano-structured semiconductor light emitting device according to another embodiment (mask structure modification) of the present invention.
- 32 to 38 are cross-sectional views of major processes for explaining a method of manufacturing a nano-structured semiconductor light emitting device according to still another embodiment of the present invention (employing a diffusion barrier film).
- FIG. 39 is a cross-sectional view showing an example of the final structure of the nano-structured semiconductor light emitting device obtained in Fig.
- FIGS. 40 to 43 are cross-sectional views for explaining a process of forming a nanocore.
- 45 is a SEM photograph of a planar arrangement and a side cross-sectional structure of a nanocore grown using the mask employed in the experimental example.
- FIG. 46 is a SEM photograph of a planar arrangement and a side cross-sectional structure of the heat-treated nanocore through an experiment.
- FIG. 46 is a SEM photograph of a planar arrangement and a side cross-sectional structure of the heat-treated nanocore through an experiment.
- 47 to 50 are cross-sectional views of main processes for explaining a method of fabricating a nanostructured semiconductor light emitting device according to another embodiment of the present invention.
- 51 and 52 show various examples of a semiconductor light emitting device package employing the semiconductor light emitting device according to an embodiment of the present invention.
- 53 and 54 show an example of a backlight unit employing a semiconductor light emitting device according to an embodiment of the present invention.
- FIG 55 shows an example of a lighting device employing a semiconductor light emitting device according to an embodiment of the present invention.
- FIG 56 shows an example of a headlamp employing a semiconductor light emitting device according to an embodiment of the present invention.
- FIGS. 1 to 5 are cross-sectional views for explaining a method of fabricating a nano-structured semiconductor light emitting device according to an embodiment of the present invention.
- the present manufacturing method starts with providing a base layer 12 made of a first conductivity type semiconductor.
- a first conductive semiconductor may be grown on the substrate 11 to provide a base layer 12.
- the substrate 11 an insulating, conductive or semiconductor substrate may be used if necessary.
- the substrate 11 may be a crystal growth substrate for growing the base layer 12.
- the substrate 11 may be selected from among sapphire, SiC, Si, MgAl 2 O 4 , MgO, LiAlO 2 , LiGaO 2 , and GaN.
- the base layer 12 not only provides a crystal growth surface for growing the nano-luminous structure 15 but also can electrically connect one end of the plurality of nano-luminous structures 15 to each other. Therefore, the base layer 12 is formed of a semiconductor single crystal having electrical conductivity.
- the base layer 12 may be a crystal satisfying Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1).
- the base layer 12 may be doped with an n-type impurity such as Si to have a specific conductivity type.
- the base layer 12 has a thickness of 1 x 10 < 18 > / cm & Or more of GaN having an n-type impurity concentration.
- the thickness of the base layer 12 provided for the growth of the nanocore 15a may be 1 ⁇ ⁇ or more.
- the thickness of the base layer 12 may be 3 to 10 ⁇ ⁇ in consideration of the subsequent electrode forming process and the like.
- the substrate 11 may be a GaN substrate which is a homogeneous substrate when the nitride semiconductor single crystal is grown using the base layer 12.
- Sapphire, silicon (Si), silicon carbide (SiC) Can be used.
- a buffer layer (not shown) may be introduced between the substrate 11 and the base layer 12 to alleviate the difference in lattice mismatch.
- the buffer layer (not shown) may be Al x In y Ga 1-xy N (0? X? 1, 0? Y? 1), in particular GaN, AlN, AlGaN, InGaN or InGaAlN, Or the composition may be gradually changed.
- a complex structure buffer layer can be used.
- a buffer layer may be formed on the substrate 11 using crystals not containing Ga to prevent reaction of Si and Ga, such as AlN or SiC.
- an AlGaN intermediate layer for controlling stress in the middle of GaN can be inserted therebetween.
- the substrate 11 may be completely or partially removed or patterned in a chip manufacturing process to improve the optical or electrical characteristics of the LED chip before or after the LED structure growth.
- the substrate in the case of a sapphire substrate, the substrate can be separated by irradiating the laser to the interface with the base layer 12 through the substrate 11, and the silicon or silicon carbide substrate is removed by a method such as polishing / etching can do.
- another supporting substrate can be used.
- a supporting substrate may be bonded using a reflective metal or a separate reflecting structure may be added to the bonding structure with the supporting substrate.
- Such a pattern may be of a size ranging from 5 nm to 500 mu m and may have a rule or an irregular pattern.
- the pattern may be formed in various shapes such as a column, an acid, and a hemisphere.
- a mask 13 having a plurality of openings H and an etch stop layer interposed therebetween is formed on the base layer 12.
- the mask 13 employed in the present embodiment includes a first material layer 13a formed on the base layer 12 and a second material layer 13b formed on the first material layer 13a, And a second material layer 13b having an etch rate greater than the etch rate of the first material layer 13a under etch conditions.
- the first material layer 13a may be provided as an etch stop layer with respect to the second material layer 13b. That is, the first material layer 13a has an etching rate lower than that of the second material layer 13b under the etching condition of the second material layer 13b.
- At least the first material layer 13a is an electrically insulating material, and if necessary, the second material layer 13b may also be an insulating material.
- the first and second material layers 13a and 13b may be formed of different materials in order to secure a desired etching rate difference.
- the first material layer (13a) is SiN
- the second material layer (13b) may be SiO 2.
- the difference in etch rate can be obtained using the difference in pore density.
- the second material layer 13b or the first and second material layers 13a and 13b are both made of a material having a porous structure and the first and second material layers 13a and 13b ) Can be ensured.
- the first and second material layers 13a and 13b may be formed of the same material.
- the first material layer 13a may be SiO 2 having a first porosity and the second material layer 13b may be made of the same SiO 2 as the first material layer 13a, 2 porosity. Accordingly, under the condition that the second material layer is etched, the first material layer 13a may have an etching rate lower than that of the second material layer 13b.
- the total thickness of the first and second material layers 13a and 13b may be designed in consideration of the height of the desired nano-light-emitting structure.
- the first material layer 13a has a thickness smaller than the thickness of the second material layer 13b.
- the etch stop level by the first material layer 13a may be a point less than 1/3 of the total height of the mask 13 from the surface of the base layer 12. In other words, the first material layer 13a may have a thickness of 1/3 or less of the total thickness of the first and second material layers 13a and 13b.
- the total height of the mask 13 and the total thickness of the first and second material layers 13a and 13b may be 1 ⁇ or more, preferably 5 to 10 ⁇ .
- the first material layer 13a may be 0.5 ⁇ ⁇ or less.
- a plurality of openings H may be formed to expose the base layer 12 region after the first and second material layers 13a and 13b are sequentially formed on the base layer 12 1b).
- the size of the opening H for exposing the surface of the base layer 12 can be designed in consideration of the size of the desired nano-light-emitting structure.
- the opening H may be formed to have a width (diameter) of 300 nm or less, more preferably 50 to 500 nm.
- the opening H of the mask 13 may be formed using a semiconductor process such as photolithography.
- a deep-etching process can be used to form openings H having a high aspect ratio.
- the aspect ratio of the opening H may be 5: 1 or more, and even 10: 1 or more.
- the deep etching process uses a dry etching process, and utilizes reactive ions generated from a plasma or an ion beam generated in a high vacuum.
- a dry etching can perform precise machining without geometric limitation of the microstructure as compared with wet etching.
- a CF-based gas may be used for etching the oxide film of the mask 13.
- an etchant in which at least one of O 2 and Ar is combined with a gas such as CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 8 , and CHF 3 may be used.
- planar shape and arrangement of such openings H can be variously implemented.
- a planar shape it can be variously implemented as a polygon, a rectangle, an ellipse, and a circle.
- the mask 13 shown in Fig. 2 may have an array of openings H having a circular cross section, as shown in Fig. 6, but may have different shapes and different arrangements, if desired.
- the mask 13 'shown in FIG. 7 may have an array of apertures H having a regular cross-section.
- the opening H shown in FIG. 2 is illustrated as a rod structure, but is not limited thereto, and may have various shapes using an appropriate etching process.
- the shape of the opening H may vary depending on the etching conditions.
- a mask having openings of different shapes is shown in Figs.
- the mask 33 made up of the first and second material layers 33a and 33b is illustrated as having a columnar opening H of a shape having a smaller width toward the bottom.
- the mask 33 'made up of the first and second material layers 33a' and 33b ' has an opening H having a columnar shape having a larger width toward the bottom, .
- a plurality of nanocores 15a are formed by growing a first conductivity type semiconductor in an exposed region of the base layer 12 so as to fill the plurality of openings H .
- the first conductivity type semiconductor of the nanocore 15a may be an n-type nitride semiconductor, for example, n-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ X + y ⁇ 1).
- the first conductivity type semiconductor constituting the nanocore may be the same material as the first conductivity type semiconductor of the base layer 12.
- the base layer 12 and the nanocore 15a may be formed of n-type GaN.
- the nitride single crystal constituting the nanocore 15a may be formed using an MOCVD or MBE process.
- the mask 13 functions as a mold of a nitride single crystal to be grown, (15a). That is, the nitride single crystal is selectively grown in the region of the base layer 12 exposed to the opening H by the mask 13 to fill the opening H, and the nitride single crystal to be filled has its opening ( H) of the semiconductor device.
- the mask 13 may be partially removed using a first material layer 13a, which is an etch stop layer, such that the sides of the plurality of nanocores 15a are exposed.
- only the second material layer 13b is removed by applying an etching process under the condition that the second material layer 13b can be selectively removed, and the first material layer 13a is removed .
- the first material layer 13a is used as an etch stop layer in the main etching process and the active layer 15b and the second conductivity type semiconductor layer 15c are prevented from being connected to the base layer 12 in a subsequent growth process. Can play a role.
- the active layer 15b and the second conductivity type semiconductor layer 15c are sequentially grown on the surfaces of the plurality of nanocores 15a.
- the nano-light-emitting structure 15 is provided with the first conductivity type semiconductor as the nanocore 15a and the active layer 15b and the second conductivity type semiconductor layer 15b surrounding the nanocore 15a, And may have a core-shell structure that is provided as a single-layer structure.
- the active layer 15b may be a multiple quantum well (MQW) structure in which a quantum well layer and a quantum barrier layer are alternately stacked, for example, a nitride semiconductor, a GaN / InGaN structure may be used, ) Structure.
- MQW multiple quantum well
- the second conductivity type semiconductor layer 15c may be a crystal that satisfies a p-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1).
- the second conductivity type semiconductor layer 15c may further include an electron blocking layer (not shown) at a portion adjacent to the active layer 15b.
- the electron blocking layer (not shown) may have a structure in which a plurality of Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0?
- the Al y Ga (1-y) N (0 ⁇ y ⁇ 1) may have a layer or more layers, and an active layer (15b) than the band gap cursor second conductivity type (p-type) semiconductor layer (15c) consisting of It is possible to prevent electrons from falling over.
- the nano-light-emitting structure 15 employed in the present embodiment is illustrated as a rod-shaped core-shell structure, but the present invention is not limited thereto and may be applied to various structures such as a pyramid structure or a structure in which a pyramid and a rod are combined It can have a different shape.
- an additional heat treatment process can be introduced to improve crystallinity.
- the surface of the nanocore is heat-treated under a predetermined condition to convert the crystal surface of the nanocore into a stable surface favorable for crystal growth such as a semi-polar or nonpolar crystal surface.
- a predetermined condition to convert the crystal surface of the nanocore into a stable surface favorable for crystal growth such as a semi-polar or nonpolar crystal surface.
- the nanostructured semiconductor light emitting device shown in FIG. 5 may have electrodes of various structures.
- Figs. 10 to 14 are cross-sectional views of major processes showing an example of the electrode forming process.
- a contact electrode layer 16 is formed on the nano-luminous structure 15 obtained in FIG. 1E.
- the contact electrode layer 16 may be obtained by forming a seed layer on the surface of the nano-light-emitting structure 15 and then performing electroplating.
- a seed layer can employ a suitable material capable of realizing ohmic contact with the second conductivity type semiconductor layer 15c.
- the ohmic contact material may include a material such as ZnO, a graphene layer, Ag, Ni, Al, Rh, Pd, Ir, Ru, Mg, Zn, / Al, Zn / Al, Pd / Ag, Pd / Al, Ir / Ag. Or two or more layers such as Ir / Au, Pt / Ag, Pt / Al, and Ni / Ag / Pt.
- a desired contact electrode layer 16 can be formed by forming a Ag / Ni / Cr layer as a seed layer using a sputtering process, and then forming Cu / Ni using electroplating.
- the contact electrode layer 16 used in the present embodiment is formed by introducing a reflective metal layer and can be understood to extract light in the substrate direction.
- the contact electrode layer 16 is not limited to ZnO, A transparent electrode material such as ITO may be used to extract light toward the nano-structure 15.
- a planarization process may be introduced to planarize the upper surface of the electrode.
- the electrode region e1 located in the region where the other electrode is to be formed is selectively removed to expose the nano-light-emitting structure 15, and then, as shown in FIG. 4C, A part of the exposed nano-light-emitting structure 15 may be removed to expose a part of the region e2 of the base layer 12.
- the process shown in FIG. 11 is an etching process for an electrode material such as a metal
- the process shown in FIG. 12 is an etching process for a semiconductor material
- the two etching processes can be performed under different conditions.
- the insulating film 17 may be formed to expose the contact regions Ta and Tb of the electrode.
- a portion of the base layer 12 may be provided in the contact region Ta of the first electrode and a portion of the contact electrode layer 16 may be provided in the contact region Tb of the second electrode.
- first and second electrodes 19a and 19b are formed to be connected to the contact regions Ta and Tb of the first and second electrodes, respectively, as shown in FIG.
- the electrode material used in this process may be a common electrode material of the first and second electrodes 19a and 19b.
- the material for the first and second electrodes 19a and 19b may be Au, Ag, Al, Ti, W, Cu, Sn, Ni, Pt, Cr, NiSn, TiW, AuSn, Lt; / RTI >
- 15 to 21 are cross-sectional views for explaining another example of the method of manufacturing a nanostructure semiconductor light-emitting device according to the present invention.
- a first conductive semiconductor may be grown on the substrate 51 to provide a base layer 52.
- the base layer 52 may be used not only as a crystal growth surface for growing the nano-luminous structure but also as a structure for electrically connecting the nano-luminous structures 55 to each other. Therefore, the base layer 52 is formed of a semiconductor single crystal having electrical conductivity.
- the substrate 51 may be a substrate for crystal growth.
- the base layer 52 may be a nitride semiconductor that satisfies Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ Type impurities.
- the substrate 51 may be sapphire, SiC, Si, MgAl 2 O 4 , MgO, LiAlO 2 , LiGaO 2 , or GaN.
- a mask 53 having a plurality of openings H and an etch stop layer interposed therebetween is formed on the base layer 52.
- the mask 53 employed in this embodiment has a first material layer 53a formed on the base layer 52 similar to the previous embodiment and a second material layer 53b formed on the first material layer 53a, And a second material layer 53b having an etch rate greater than the etch rate of the material layer 53a.
- the first material layer 53a may be provided as an etch stop layer.
- the first and second material layers 53a and 53b may be different materials to secure a desired etching rate difference.
- the first material layer (53a) is SiN
- the second material layer (53b) may be SiO 2.
- the second material layer 53b or the first and second material layers 53a and 53b may be formed of a material having a porous structure, and the difference in the porosity may be used to secure the difference in etch rate.
- the first and second material layers 53a and 53b may be formed of the same material.
- each opening H may be formed to expose the base layer 52 region.
- the size of each opening H that exposes the surface of the base layer 52 can be designed in consideration of the size of the desired nano-light-emitting structure.
- the opening H may have a width (diameter) of 600 nm or less, more preferably 50 to 500 nm.
- the region where the opening H is formed is a region where the nanocore, that is, the nano-light emitting structure is to be grown
- the regions E1 and E2 in which the electrode is to be formed are set in advance, and the regions E1, E2 may not be provided with the opening H.
- the process of removing the nano-light-emitting structure in the later electrode formation step may be omitted.
- the opening H of the mask 53 may be formed using a semiconductor process such as photolithography. For example, a deep-etching process can be used to form openings H having a high aspect ratio.
- the aspect ratio of the opening H may be 5: 1 or more, and even 10: 1 or more.
- the opening H in the first and second material layers 53a and 53b may have a width that becomes smaller as it goes toward the base layer. Reference).
- a plurality of nanocores 55a are formed by growing a first conductivity type semiconductor in an exposed region of the base layer 52 so as to fill the plurality of openings H .
- the first conductive semiconductor of the nanocore 55a may be an n-type nitride semiconductor, for example, an n-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ X + y ⁇ 1).
- the first conductivity type semiconductor constituting the nanocore 55a may be the same material as the first conductivity type semiconductor of the base layer 52.
- the base layer 52 and the nanocore 55a may be formed of n-type GaN.
- the nitride single crystal constituting the nanocore 55a may be formed using an MOCVD or MBE process.
- the mask 53 functions as a mold of the nitride single crystal to be grown, and the nanocore 55a corresponding to the shape of the opening, Can be provided. That is, the nitride single crystal is selectively grown in the region of the base layer 52 exposed to the opening H by the mask 53 to fill the opening H, and the nitride single crystal to be filled has a And may have a shape corresponding to the shape.
- the mask 53 may be partially removed using the first material layer 53a, which is the etch stop layer, so that the side surfaces of the plurality of nanocores 55a are exposed .
- the second material layer 53b is removed by etching under the condition that the second material layer 53b can be selectively removed, so that the first material layer 53a may remain.
- the first material layer 53a is used as an etch stop layer in the main etching process and prevents the active layer 55b and the second conductivity type semiconductor layer 55c from being connected to the base layer 52 in a subsequent growth process. Can play a role.
- an additional heat treatment process can be introduced to improve the crystallinity.
- 19 shows a nanocore 55a 'which is heat-treated to improve the crystallinity of the surface.
- the surface of the nanocore 55a is heat-treated under a certain condition to convert the crystal surface of the nanocore 55a into a stable surface favoring crystal growth such as a semi-polar or non- have.
- a process can be described with reference to FIGS. 22 and 23.
- 22 and 23 are schematic views for explaining a heat treatment process which can be applied in the process of FIG.
- Fig. 22 can be understood as the nanocore 55a obtained in Fig.
- the nanocore 55a has a crystal face defined by the shape of the opening.
- the surface of the thus obtained nanocore 55a has a relatively unstable crystal face, and may not be favorable for subsequent crystal growth.
- the side surface of the nanocore 55a may have a curved surface other than a specific crystal surface.
- a nanocore When such a nanocore is heat-treated, unstable crystals on the surface thereof are rearranged to have a stable crystal plane, such as semi-polar or non-polar, as shown in Fig.
- the heat treatment can be carried out at a temperature of 600 ° C or higher, and in a specific example, at 800 to 1200 ° C for several seconds to several tens of minutes (1 second to 60 minutes), whereby a desired stable crystal plane can be obtained.
- the substrate temperature is lower than 600 ° C, the crystal growth and rearrangement of the nanocrystals are difficult, and the heat treatment effect is difficult to expect.
- nitrogen (N) may be evaporated from the GaN crystal surface, . Further, it is difficult to expect a sufficient heat treatment effect in a time shorter than 1 second, and heat treatment for several tens of minutes, for example, longer than 60 minutes, may reduce the efficiency of the manufacturing process.
- the columnar nanocore 55a shown in FIG. 6A is grown in the above- ,
- the curved surface (side surface) which is an unstable crystal plane can be converted into a hexagonal crystal pillar (55a 'in Fig. 23) having a non-polar surface (m plane) which is a stable crystal plane.
- the stabilization process of such a crystal face can be realized by a high-temperature heat treatment process.
- the heat treatment process may be performed in an atmosphere in which the source gas remains in the chamber, or may be heat-treated under the condition of intentionally supplying a small amount of the source gas.
- TMGa and NH 3 remain in the case of the MOCVD chamber, and partial regrowth is performed so that the source gas reacts with the surface of the nanocore by heat treatment in the residual atmosphere to have a stable crystal plane Lt; / RTI > Due to such regrowth, the width of the heat treated nanocore 55a 'may be somewhat larger than the width of the nanocore 55a before heat treatment (see FIGS. 22 and 23).
- introduction of an additional heat treatment process can contribute to enhancement of the crystallinity of the nanocore. That is, through such a heat treatment process, non-uniformity (eg, defects) existing on the surface of the nanocore after removing the mask can be removed, and stability of the crystal can be greatly improved through rearrangement of the internal crystal .
- a heat treatment process may be performed under conditions similar to the growth process of the nanocore in the chamber after removing the mask.
- the heat treatment temperature for example, the substrate temperature
- the heat treatment temperature can be performed between 800 and 1200 ° C, but a similar effect can be expected in a heat treatment process at 600 ° C or higher.
- the active layer 55b and the second conductivity type semiconductor layer 55c are sequentially grown on the surfaces of the plurality of nanocores 55a '.
- the nano-light-emitting structure 55 includes the nanocrystals 55a ', the active layer 55b surrounding the nanocores 55a', and the second conductive semiconductor layer 55c Shell structure with a shell layer formed thereon.
- the active layer 55b may be a multi quantum well (MQW) structure in which a quantum well layer and a quantum barrier layer are alternately stacked, for example, a nitride semiconductor, a GaN / InGaN or GaN / AlGaN structure may be used, A quantum well (SQW) structure may be used.
- MQW multi quantum well
- the second conductive type semiconductor layer 55c may be a crystal that satisfies a p-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1).
- the second conductivity type semiconductor layer 55c may further include an electron blocking layer (not shown) at a portion adjacent to the active layer 55b.
- the electron blocking layer (not shown) may have a structure in which a plurality of Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1) (P-type) semiconductor layer 55c having a bandgap larger than that of the active layer 55b, and may have a layer of one or more layers of Al y Ga (1-y) N Prevent electrons from falling.
- the nanocore 55a ' may be divided along the growth direction into a main portion providing a side having a first crystal plane and an upper portion providing a surface having a second crystal plane different from the first crystal plane.
- the side surface of the main portion has a crystal plane perpendicular to the growth surface of the base layer 52, that is, a non-polar m surface, And has an opposite r-plane.
- the surface of the nanocore 55a ' may have a plurality of different crystal planes.
- the composition (in particular, the indium content) of the active layer 55b may vary depending on each crystal plane . Further, the active layer portion formed at the upper end portion may have a relatively thin thickness.
- a contact electrode 56 may be formed on the nano-light-emitting structure 55, and an insulating protective layer 57 may be further formed on the contact electrode 56.
- the contact electrode 56 may be formed of an ohmic contact material that can realize Ohmic contact with the second conductive type semiconductor layer 55c.
- it may include at least one of Ag, Ni, Al, Rh, Pd, Ir, Ru, Mg, Zn, Pt and Au and may be provided as a single layer or a plurality of layers.
- the contact electrode 56 may employ a transparent electrode material such as ITO, and ZnO or graphene may be used as needed.
- the insulating protective layer 57 can be used as an electrically insulating material capable of providing a passivation structure by a semiconductor process.
- an insulating protective layer such as SiO 2 or SiN x may be used. More specifically, as the insulating protective layer 57, so as to easily realize the filling of the space between the nano-emitting structure (55), TEOS (TetraEthylOrthoSilane), BPSG (BoroPhospho Silicate Glass), CVD-SiO 2, SOG (Spin- on Glass, and SOD (Spin-on Delectric) materials can be used.
- the contact electrode 56 is provided in the form of a thin layer along the surface of the nano-light-emitting structure 55, and the insulating protection layer 57 serving as the passivation layer is filled.
- the contact electrode may be formed as a thick film so as to fill the space between the nano-light-emitting structures.
- heat treatment process introduced in the above-described embodiment is described as being performed after removal of the mask 53, in the growth process of the nanocore 55a before the mask removal, or after the completion of growth of the nanocore 55a and It can also be applied before mask removal.
- the heat treatment step introduced before removing the mask can be performed under conditions similar to the growth temperature, and a sufficient effect can be expected even in a time shorter than the heat treatment step time after relatively removing the mask. It can be understood that the heat treatment process before removing the mask improves the crystallinity of the nanocore 55a 'in terms of crystal rearrangement. This will be described in detail with reference to the following experimental examples.
- the nanostructured semiconductor light emitting device shown in FIG. 21 can have electrodes formed in various structures.
- Figs. 24 to 27 are cross-sectional views of main processes showing an example of the electrode forming process.
- the insulating protective layer 57 may be selectively removed to expose a portion O of the base layer 52, as shown in FIG.
- the exposed region O of the base layer 52 may provide a region where the first electrode is to be formed.
- the present removal process can be implemented by an etching process using a photolithography process.
- a process of removing the nano-light-emitting structure is also required.
- the core 55a is not grown, there may be no nano-luminescent structures 55 to be removed in the present process.
- a photoresist PR having first and second openings e1 and e2 can be formed.
- the first and second openings e1 and e2 may define a formation region of the first and second electrodes, respectively.
- the first opening e1 may expose a portion of the base layer 52 and the second opening e2 may expose a portion of the contact electrode 56.
- first and second electrodes 59a and 59b may be formed in the first and second openings e1 and e2.
- the electrode material used in this process may be a common electrode material of the first and second electrodes 59a and 59b.
- the material for the first and second electrodes 59a and 59b may be Au, Ag, Al, Ti, W, Cu, Sn, Ni, Pt, Cr, Sn, TiW, AuSn, . ≪ / RTI >
- a passivation layer 58 may be additionally formed.
- the passivation layer 58 may be provided as a protective layer for protecting the nanostructured structure together with the insulating protective layer 57.
- the passivation layer 58 not only covers and protects the exposed semiconductor region, but also can firmly hold the first and second electrodes 59a and 59b.
- the passivation layer 58 may be made of the same or similar material as the insulating protective layer 57.
- the mask adopted in the above-described embodiment is illustrated as being composed of two material layers, the present invention is not limited thereto and may be embodied in the form of employing three or more material layers.
- FIGS. 28 to 31 are cross-sectional views for explaining a method of manufacturing a nano-structured semiconductor light emitting device according to another embodiment (mask structure modification) of the present invention.
- a base layer 62 is provided on the substrate 61, and a mask (not shown) having a plurality of openings H and having an etch stop layer 63b is formed on the base layer 62 63 are formed.
- the mask 63 employed in the present embodiment includes first to third material layers 63a, 63b and 63c sequentially formed on the base layer 62.
- the second material layer 63b may be provided as an etch stop layer and is made of a material different from the first and third material layers 63a and 63c. If desired, the first and third material layers 63a and 63c may be made of the same material.
- At least the second material layer 63b has an etching rate lower than the etching rate of the third material layer 63c in the etching condition of the third material layer 63c, and thus can act as an etch stop layer.
- At least the first material layer 63a is an electrically insulating material, and the second or third material layer 63b and 63c may be an insulating material if necessary.
- the first to third material layers 63a, 63b, and 63c may be different materials for a difference in a desired etching rate.
- the first and the second material layer (63b) is SiN
- the first and third material layers (63a, 63c) may be SiO 2.
- the difference in etch rate can be realized using the pore density.
- the second and third material layers 63b and 63c may be formed of the same material having a different void density.
- the total thickness of the first to third material layers 63a, 63b and 63c can be designed in consideration of the height of the desired nano-light-emitting structure.
- the first and second material layers 63a and 63b have a thickness smaller than the thickness of the third material layer 63c.
- the etch stop level by the second material layer 63b is determined by the total height of the mask 63 from the surface of the base layer 62 and the total thickness of the first to third material layers 63a, 63b, It can be located at 1/3 or less.
- the total height of the mask 63 and the total thickness of the first to third material layers 63a, 63b and 63c may be 1 ⁇ ⁇ or more, preferably 5 to 10 ⁇ ⁇ .
- the thickness of the first and second material layers 63a and 63b may be 0.5 ⁇ or less.
- the first to third material layers 63a to 63c are successively formed on the base layer 62 and then a plurality of openings H are formed by using a photolithography process using a photoresist PR Thereby exposing the base layer 62 region (FIG. 8A).
- the size of each opening H can be designed in consideration of the size of the desired nano-light-emitting structure.
- the opening H may be formed to have a width (diameter) of 600 nm or less, further, 50 to 500 nm.
- the opening H may be formed using a semiconductor process such as photolithography and may form an opening H having a high aspect ratio, for example, using a deep etching process.
- the aspect ratio of the opening H may be 5: 1 or more, and even 10: 1 or more.
- a plurality of nanocores 65a are formed by growing a first conductivity type semiconductor in an exposed region of the base layer 62 so that the plurality of openings H are filled.
- the first conductive semiconductor of the nanocore 65a may be an n-type nitride semiconductor, for example, an n-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ X + y ⁇ 1).
- the first conductivity type semiconductor constituting the nanocore 65a may be the same material as the first conductivity type semiconductor of the base layer 62.
- the base layer 62 and the nanocore 65a may be formed of n-type GaN.
- the nitride single crystal constituting the nanocore 65a may be formed using an MOCVD or MBE process, and the mask 63 functions as a mold of the nitride single crystal to be grown, and the nanocore 65a corresponding to the shape of the opening, Can be provided. That is, the nitride single crystal is selectively grown in the region of the base layer 62 exposed to the opening H by the mask 63 to fill the opening H, and the nitride single crystal to be filled has a And may have a shape corresponding to the shape.
- the mask 63 is partially removed using the second material layer 63b, which is the etch stop layer, so that the side surfaces of the plurality of nanocore 65a are exposed.
- the third material layer 63c is removed by applying an etching process under the condition that the third material layer 63c can be selectively removed, and the first and second material layers 63a, 63b may remain.
- the second material layer 63b is used as an etch stop layer in the etching process. In the subsequent growth process together with the first material layer 63a, the active layer 65b and the second conductivity type semiconductor layer 65c Can be prevented from being connected to the base layer (62).
- the quality of the crystal of the nanocore 65a can be improved by applying the heat treatment process described with reference to FIG. 22 and FIG.
- an active layer 65b and a second conductivity type semiconductor layer 65c are successively grown on the surface of the plurality of nanocore 65a.
- the nano-light-emitting structure 65 is provided with the first conductivity type semiconductor as the nanocore 65a, the active layer 65b surrounding the nanocore 65a, and the second conductivity type semiconductor layer 65b, And may have a core-shell structure that is provided as a single-layer structure.
- the active layer 65b may be a multiple quantum well (MQW) structure in which a quantum well layer and a quantum barrier layer are alternately stacked, for example, a nitride semiconductor, a GaN / InGaN structure may be used, ) Structure.
- MQW multiple quantum well
- the second conductivity type semiconductor layer 65c may be a crystal that satisfies a p-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1).
- the second conductive semiconductor layer 65c may further include an electron blocking layer (not shown) at a portion adjacent to the active layer 65b.
- the electron blocking layer (not shown) may have a structure in which a plurality of Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1) (P-type) semiconductor layer 65c having a bandgap larger than that of the active layer 65b, and may be formed of Al y Ga (1-y) N Prevent electrons from falling.
- the nano-light-emitting structure 65 employed in the present embodiment is illustrated as a core-shell structure in the form of a rod, but the present invention is not limited thereto.
- a structure in which a pyramid structure or a pyramid- It can have a different shape.
- the mask is used as a mold for nanocore growth, so that the surface of the nanocore to be grown next is in direct contact with the mask.
- the semiconductor growth process for the nanocore is performed at a high temperature, the components of the mask may diffuse into the nanocore, causing a problem of deteriorating crystallinity.
- the present inventors have additionally proposed a method of employing a diffusion barrier film on the opening side wall of the mask.
- 32 to 38 are cross-sectional views of major processes for explaining a method of manufacturing a nano-structured semiconductor light emitting device according to still another embodiment of the present invention (employing a diffusion barrier film).
- a base layer 72 is provided on the substrate 71 and a mask having a plurality of openings H and having an etch stop layer 73b is formed on the base layer 72 73 are formed.
- the mask 73 employed in this embodiment has a structure similar to the mask 63 described in the foregoing embodiment. That is, the mask 73 includes first to third material layers 73a, 73b, and 73c sequentially formed on the base layer 72.
- the second material layer 73b may be provided as an etch stop layer and may be made of a different material than the first and third material layers 73a and 73c.
- the first and third material layers 73a and 73c may be formed of the same material.
- At least the second material layer 73b has an etching rate lower than that of the third material layer 73c, and thus can act as an etch stop layer.
- At least the first material layer 73a is an electrically insulating material, and the second and third material layers 73b and 73c may be an insulating material if necessary.
- the first to third material layers 73a, 73b, and 73c may be different materials for different etching rates. Alternatively, the difference in etch rate can be realized using the pore density. In this case, the second and third material layers 73b and 73c may be formed of the same material having a different void density.
- Figs. 33 and 34 illustrate a step of forming a diffusion preventing film on the side wall of the opening.
- a material film 74 'for the diffusion preventing film is formed on the surface of the mask 73.
- the material film 74 'used as the diffusion preventing film may be made of a material having higher thermal stability than the material used for the mask 73 (particularly, the third material layer 73c). For example, TiN, TaN, and combinations thereof may be used as such material films. This material film 74 'is more excellent in thermal stability than a conventional mask such as SiO 2 and can be advantageously used as a diffusion barrier film. ,
- a desired diffusion prevention film 74 can be obtained by selectively removing the material film 74 'so as to remain only on the inner sidewalls of the opening H, as shown in FIG.
- the diffusion barrier film 74 can be obtained by removing the upper surface of the base layer 72 and the portion located on the exposed region of the base layer 72. Part of the base layer 72, which is located in the exposed region, must be removed, in particular, since it is difficult to carry out subsequent crystal growth if the diffusion preventing film remains in the exposed region of the base layer 72.
- This selective removal process is performed in such a manner as to remove the material film located on the top surface of the mask 73 and the exposed region of the base layer 72 using anisotropic etching such as dry etching since the sidewalls of the opening H are nearly vertical .
- a plurality of nanocores 75a are formed by growing the first conductivity type semiconductor in the exposed region of the base layer 72 so that the plurality of openings H are filled .
- the first conductivity type semiconductor of the nanocore 75a may be an n-type nitride semiconductor, for example, an n-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ X + y ⁇ 1).
- the nitride single crystal constituting the nanocore 75a may be formed using an MOCVD or MBE process.
- the mask 73 functions as a mold of the nitride single crystal to be grown, (75a).
- the mask 73 may be partially removed using the second material layer 73b, which is the etch stop layer, so that the side surfaces of the plurality of nanocores 75a are exposed. have.
- only the third material layer 73c is removed by an etching process under the condition that the third material layer 73c can be selectively removed, and the first and second material layers 73a, 73b may remain.
- the diffusion barrier layer 74 may be removed from the exposed surface of the nanocore 75a.
- the diffusion barrier layer 74 is a relatively stable material, the diffusion barrier layer 74 may remain on the surface of the nanocore 75a without being removed in the etching process for removing the third material layer 73c. In this way, when the diffusion prevention film 74 remains, it is difficult to proceed with the subsequent crystal growth step, so that the diffusion preventing film 74 can be removed so that the crystal face of the nanocore 75a is exposed.
- the diffusion preventing film 74 may be removed by performing a separate etching process for removing the material constituting the diffusion preventing film 74. Even if this removal process is applied, the portion of the diffusion barrier film located between the remaining mask (the first and second material layers) and the nanocore 75a may remain without being removed. Since this portion is not used as a crystal growth surface, it does not adversely affect the nanostructure semiconductor light emitting device.
- the crystallization quality of the nanocore 75a can be improved by applying the heat treatment process described with reference to FIGS. 22 and 23.
- the active layer 75b and the second conductivity type semiconductor layer 75c are successively grown on the surfaces of the plurality of nanocores 75a.
- the nano-light-emitting structure 75 is provided with the first conductivity type semiconductor as the nanocore 75a and the active layer 75b and the second conductivity type semiconductor layer 75b surrounding the nanocore 75a, And may have a core-shell structure that is provided as a single-layer structure.
- the active layer 75b may be a multiple quantum well (MQW) structure in which a quantum well layer and a quantum barrier layer are alternately stacked, for example, a nitride semiconductor, a GaN / InGaN structure may be used, ) Structure.
- MQW multiple quantum well
- the second conductivity type semiconductor layer 75c may be a crystal that satisfies p-type Al x In y Ga 1-xy N (0? X ⁇ 1, 0? Y ⁇ 1, 0? X + y ⁇ 1).
- the second conductive semiconductor layer 75c may further include an electron blocking layer (not shown) at a portion adjacent to the active layer 75b.
- Fig. 39 shows an example of a final structure of the nano-structured semiconductor light emitting device obtained in Fig. 38, as an example of a nano-structured semiconductor light emitting device employing another electrode structure.
- the nanostructured semiconductor light emitting device 70 includes a plurality of nano-light emitting structures 75 formed on a substrate 71.
- the nano-light-emitting structure 75 may be the nano-light-emitting structure 75 illustrated and described with reference to FIG.
- the residual diffusion preventing film 74 " may include a residual diffusion preventing film 74 " positioned between the nanocore 75c and the inner side wall of the opening H.
- the contact electrode layer 76 is formed in a state filled between the nano-light emitting structures 75.
- the contact electrode layer 76 may form an ohmic contact with the second conductivity type semiconductor layer 75c and may structurally stabilize the nano-light emitting structure 75.
- the nano-structured semiconductor light emitting device 70 includes first and second electrodes 79a and 79b connected to the base layer 72 of the first conductivity type semiconductor and the contact electrode layer 76, respectively.
- Figs. 40 to 43 are cross-sectional views of major processes for explaining a process of forming a nano-luminescent structure using the mask 83 of the specific example.
- the nano core 85a can be grown on the base layer 82 by using the mask 83.
- the mask 83 has an opening H with a width that narrows downward.
- the nanocore 85a may be grown in a shape corresponding to the shape of the opening H.
- one or more heat treatment processes during growth can be introduced.
- the top surface of the nanocore 85a during growth is rearranged to the crystal plane of the hexagonal pyramid, so that a more stable crystal structure can be obtained and high quality of the subsequent grown crystal can be ensured.
- Such a heat treatment process can be performed under the temperature conditions described above.
- the process temperature may be the same as or similar to the growth temperature of the nanocore 85a.
- it can be performed in such a manner that the metal source such as TMGa is stopped while maintaining the pressure / temperature at the same or similar level as the growth pressure and temperature of the nanocore 85a in the NH 3 atmosphere.
- This heat treatment process can last from a few seconds to several tens of minutes (e.g., 5 seconds to 30 minutes), but sufficient effect can be obtained even with a duration of about 10 seconds to about 60 seconds.
- the heat treatment process introduced in the growth process of the nanocore 85a can prevent the deterioration of crystallinity caused when the nanocore 85a grows at a high speed, .
- the time and frequency of the annealing process for this stabilization can be varied according to the height and diameter of the final nanocore. For example, when the width of the opening is 300 to 400 nm and the height of the opening (mask thickness) is about 2.0 ⁇ ⁇ , a stabilization time of about 10 seconds to about 60 seconds at about 1.0 ⁇ ⁇ , Of the core can be grown. Of course, this stabilization process may be omitted depending on the core growth conditions.
- a current suppressing intermediate layer 84 which is a high-resistance layer, may be formed on the top of the nanocore 85a.
- the current suppressing intermediate layer 84 may be formed on the upper surface of the nanocore 85a with the mask 83 left intact after the nanocore 85a is formed at a desired height. As described above, the current-suppressing intermediate layer 84 can be easily formed on a desired region (upper surface) of the nanocore 84 without using a mask 83 for forming a separate mask.
- the current blocking interlayer 84 may be a semiconductor layer that is not intentionally doped or doped with a second conductivity type impurity opposite to the nanocore 85a.
- the current control interlayer 84 may be undoped GaN or GaN doped with Mg, which is a p-type impurity. In this case, it is possible to continuously form the nanocore 85a and the current-suppressing intermediate layer 84 by switching only the kind of impurity in the same growth step.
- the current-suppressing intermediate layer 84 has a thickness t of about 200 nm to about 300 nm, And this current suppressing intermediate layer can effectively block leakage currents of several mu A or more.
- the process of introducing the current-suppressing intermediate layer can be realized in a simple manner.
- the mask 83 is removed to the first material layer 83a, which is the etch stop layer, so that the side surfaces of the plurality of nanocore 85a are exposed.
- the first material layer 83a can be left by applying an etching process in which the second material layer 83b can be selectively removed .
- the remaining first material layer 83a may prevent the active layer and the second conductivity type semiconductor layer from being connected to the base layer 82 in a subsequent growth process.
- an additional heat treatment process can be introduced to improve the crystallinity.
- the surface of the nanocore 85a may be heat-treated under a predetermined condition to convert the unstable crystal plane of the nanocore 85a to a stable crystal plane (see FIGS. 22 and 23 ).
- the nanocore 85a since the nanocore 85a is grown in an opening having an inclined side wall, the nanocore 85a has a shape having an inclined side wall corresponding to the shape thereof.
- the nanocore 85a ' may undergo regrowth with rearrangement of crystals and may have a diameter (or width) that is substantially uniform and larger than the diameter of the opening H.
- the upper end of the nanocore 85a immediately after growth may have an incomplete hexagonal pyramid shape, but the nanocore 85a 'after the heat treatment process may be changed into a hexagonal pyramid shape having a uniform surface.
- the nanocore 85a having a non-uniform width after removal of the mask can be re-grown (and / or rearranged) as a nanocore 85a 'of a hexagonal pyramid column having a uniform width through a heat treatment process.
- the SiN layer (“a" in FIG. 44) was formed to a thickness of about 100 nm, and the SiO 2 layer (“b" in FIG. 44) was formed to a thickness of 2500 nm.
- the opening of the mask was formed by etching a photoresist (a layer located on "b” in FIG. 44) process with a plasma of C 4 F 8 , O 2 and Ar combined for about 5 minutes. 44 is an SEM photograph of a section of the opening obtained through this process. As shown in Fig. 44, the opening of the mask has a shape that becomes narrower toward the bottom.
- a nanocore was grown on the opening of the mask using an MOCVD process.
- TMGa and NH 3 were used as the source gas, and the nanocores were grown for about 20 minutes while the temperature of the substrate was maintained at about 1100 ° C.
- a stabilization step (heat treatment step) of the nanocore during growth was further performed. That is, when grown to about 1.0 ⁇ m height of the mid-point (10 minutes) of the desired nano-core, stops the TMGa source supply, and the NH 3 in the similar atmosphere for about 30 seconds to about 50 seconds and the temperature of the substrate during growth Heat treatment was performed at a temperature (about 1100 ° C). Next, regrowth of nanocores was carried out under conditions similar to the growth conditions before the heat treatment process.
- the SiO 2 layer ("b" in FIG. 44) in the mask was removed.
- the nanocore has a cylindrical shape with a sloped side wall corresponding to the shape of the opening (see FIG. 45).
- the cylindrical core of the nanocore was confirmed to have a height of about 2467 nm and a diameter of about 350 nm.
- a heat treatment process was applied. That is, heat treatment was performed for about 20 minutes (15 minutes to 25 minutes) at a substrate temperature of about 1100 ° C (1000 to 1200 ° C).
- the nanocores were re-grown together with the rearrangement of crystals so that the diameters that were not uniform in the height direction became almost uniform and the top of the nanocore was also incomplete hexagonal pyramid shape.
- the hexagonal pyramid shape See Fig. 46).
- the diameter (w1) of the nanocore was 350 nm before the annealing process, but increased by about 60 nm, and the width (w2: a hexagonal confronting interval) was increased to about 410 nm. It was confirmed that the height of the nanocore was increased by about 3 nm, and the nanocrystal was grown from about 2467 nm to about 2470 nm.
- the nanocore having a non-uniform width after removal of the mask was re-grown (and rearranged) into a hexagonal pyramid column structure having a uniform width through the heat treatment process.
- the nanocore size and shape after regrowth can be relatively changed depending on the heat treatment temperature (i.e., the substrate temperature) and the heat treatment time and whether or not the source gas is supplied or supplied.
- heat treatment temperature i.e., the substrate temperature
- the heat treatment time may cause crystal rearrangement on the surface of the nanocore, thereby reducing the size change of the nanocore due to the etching effect (i.e., N evaporation) .
- the change in diameter of the nanocore can be maintained at a level of 50% or less considering the process time, conditions, and cost.
- the uniformity of the diameter (or width) of the plurality of nanocores through the heat treatment process can be maintained at 95% or more. In this case, the diameters of the respective nanocores grown in the group having the same opening size of the mask can be formed at substantially the same level as each other.
- nanostructured semiconductor light emitting device fabrication method for growing the nanocores by using the mask having the openings as the mold structure has been described with reference to the above embodiment, the fabrication method of the nanostructured semiconductor light emitting device can be modified or improved to various specific examples.
- At least a portion of the plurality of nanocores may be designed such that at least one of the cross-sectional area (or diameter) and the gap is different as compared to the other nanocore.
- a mask 93 having a plurality of openings H and an etch stop layer interposed therebetween is formed on a base layer 92 formed on a substrate 91.
- a mask 93 employed in this embodiment includes a first material layer 93a formed on the base layer 92 and a second material layer 93b formed on the first material layer 93a And a second material layer 93b having an etch rate greater than the etch rate of the first material layer 93a.
- the openings H may be formed in different patterns. Specifically, this embodiment is formed into three different groups.
- the openings of the second group A2 have the same width d1 as the openings d1 of the first group A1 but are larger than the openings w1 of the openings of the first group A1
- the openings of the third group A3 have the same width w1 as the openings w1 of the first group A1 but are larger than the openings d1 of the openings of the first group A1 And an interval d2.
- the larger the distance between the openings means that the amount of contact of the source gas with respect to the same area is relatively increased. Therefore, the growth rate of the nanocore 95a is relatively faster and the width of the opening is larger. The contact amount of the source gas is reduced, so that the growth rate of the nanocore 95a can be relatively slow.
- the shapes of the openings are different from the openings.
- the openings may be formed in two or more groups with different openings and widths.
- light emitted from two or more groups may have a complementary relationship with each other, or white light may be emitted when they are combined with each other.
- the other group can design to emit yellow light.
- any one of the spacing of the openings and the width of the openings may be designed to emit blue, green, and red light, respectively.
- the active layer emitting light of the blue series is obtained in a group in which the interval of the openings is relatively small, and the active layer emitting light of the red series has a relatively large interval Can be obtained from a large group.
- the thickness of the active layer and / or the second conductivity type semiconductor layer also tends to increase. Therefore, in general, the diameter of the red-based nano-light-emitting structure (nanocore, active layer, second conductivity type semiconductor layer) is larger than the diameter of the nano-luminous structure emitting blue and green light, It may be larger than the diameter of the nano-light-emitting structure.
- the heights of the nanocores 95a formed in the three groups are different from each other in height due to the difference in growth rate of the nanocore 95a due to the widths and the intervals of the openings, .
- planarization process since the mask 93 is used to support the nanocore 95a, a desired planarization process can be easily performed without damaging the nanocore 95a.
- the planarization process may be performed after forming the core-shell structure and the contact electrode, and in this case, the planarization process applied in this step may be omitted.
- the mask 93 is partially removed so that the side surface of the planarized nanocore 95a is exposed. That is, only the second material layer 93b may be removed through the removal process to leave the first material layer 93a.
- the active layer 95b and the second conductivity type semiconductor layer 95c are successively grown on the surfaces of the plurality of nanocores 95a.
- the nano-light-emitting structure 95 is provided with the first conductivity type semiconductor as the nanocore 95a, the active layer 95b surrounding the nanocore 95a, and the second conductivity type semiconductor layer 95c, And may have a core-shell structure that is provided as a single-layer structure.
- the nano-light-emitting structure 95 employed in the present embodiment is illustrated as a rod-shaped core-cell structure, but is not limited thereto and may have various other shapes such as a pyramid structure or a structure in which a pyramid and a rod are combined have.
- the planarization process of FIG. 15C may be omitted, and a white light emitting device may be fabricated using a nano-light-emitting structure having a core-shell structure using nanocores 95a having different heights .
- the growth process of the nanocore and the electrode formation process of the light emitting structure may proceed in the same manner as described in the other embodiments described above.
- the nano semiconductor light emitting device according to the above-described embodiment may be implemented in various packages.
- 51 and 52 show an example of a package using the semiconductor light emitting element described above.
- the semiconductor light emitting device package 500 shown in FIG. 51 may include a semiconductor light emitting device 501, a package body 502, and a pair of lead frames 503.
- the semiconductor light emitting device 501 may be the nano semiconductor light emitting device described above.
- the semiconductor light emitting device 501 may be mounted on the lead frame 503 and electrically connected to the lead frame 503 through the wire W.
- the semiconductor light emitting element 501 may be mounted in an area other than the lead frame 503, for example, the package body 502.
- the package body 502 may have a cup shape so as to improve light reflection efficiency.
- a plug 505 made of a light-transmitting material is disposed in the reflective cup to seal the semiconductor light emitting device 501 and the wire W, Can be formed.
- the semiconductor light emitting device package 600 shown in FIG. 52 may include a semiconductor light emitting device 601, a mounting substrate 610, and a plug 603.
- the wavelength converting portion 602 may be formed on the surface and the side surface of the semiconductor light emitting device 601.
- the semiconductor light emitting device 601 may be mounted on a mounting substrate 610 and electrically connected to the mounting substrate 610 through a wire W.
- the mounting substrate 610 may include a substrate body 611, an upper electrode 613 and a lower electrode 614 and a penetrating electrode 612 connecting the upper electrode 613 and the lower electrode 614.
- the mounting substrate 610 may be provided as a PCB, MCPCB, MPCB, FPCB, or the like, and the structure of the mounting substrate 610 may be applied in various forms.
- the wavelength converter 602 may include a phosphor, a quantum dot, and the like.
- the sealing member 603 may be formed in a dome-shaped lens structure having a convex upper surface. However, according to the embodiment, by forming the surface of the sealing member 603 with a convex or concave lens structure, the orientation of light emitted through the upper surface of the sealing member 603 It is possible to adjust the angle.
- nanostructured semiconductor light emitting device according to the above-described embodiment and the package having the same may be advantageously applied to various application products.
- Figs. 53 and 54 show an example of a backlight unit employing a nanostructured semiconductor light emitting device according to an embodiment of the present invention.
- a backlight unit 1000 includes a light source 1001 mounted on a substrate 1002, and at least one optical sheet 1003 disposed thereon.
- the light source 1001 can use the above-described semiconductor light emitting device or a package including the semiconductor light emitting device.
- the backlight unit 2000 of another example shown in FIG. 54 is mounted on the substrate 2002
- the light source 2001 emits light in the lateral direction, and the thus emitted light is incident on the light guide plate 2003 and can be converted into a form of a surface light source.
- Light passing through the light guide plate 2003 is emitted upward and a reflective layer 2004 may be disposed on the lower surface of the light guide plate 2003 to improve light extraction efficiency.
- 55 is an exploded perspective view showing an example of a lighting device employing a semiconductor light emitting device according to an embodiment of the present invention.
- the lighting device 3000 shown in FIG. 55 is illustrated as a bulb-type lamp as an example, and includes a light emitting module 3003, a driving part 3008, and an external connection part 5010.
- the light emitting module 3003 may include a light source 3001 having the above-described semiconductor light emitting device package structure or a similar structure, and a circuit board 3002 on which the light source 3001 is mounted.
- the first and second electrodes of the semiconductor light emitting element described above may be electrically connected to the electrode pattern of the circuit board 3002.
- one light source 3001 is illustrated as being mounted on the circuit board 3002, but a plurality of light sources 3001 may be mounted as needed.
- the outer housing 3006 may include a heat radiating fin 3005 that may act as a heat dissipating portion and may be in direct contact with the light emitting module 3003 to improve the heat dissipating effect and a heat dissipating fin 3005 surrounding the side of the lighting device 3000 .
- the cover portion 3007 is mounted on the light emitting module 3003 and may have a convex lens shape.
- the driving unit 3008 may be mounted on the inner housing 3009 and connected to an external connection unit 3010 such as a socket structure to receive power from an external power source.
- the driving unit 3008 converts the current into a proper current source capable of driving the semiconductor light emitting device 3001 of the light emitting module 3003 and provides the current source.
- a driver 3008 may be composed of an AC-DC converter or a rectifying circuit component or the like.
- FIG 56 shows an example in which the semiconductor light emitting device according to the embodiment of the present invention is applied to a headlamp.
- a head lamp 4000 used as a vehicle light includes a light source 4001, a reflecting portion 4005, and a lens cover portion 4004, and the lens cover portion 4004 includes a hollow guide A lens 4003, and a lens 4002.
- the light source 4001 may include the above-described semiconductor light emitting device or a package having the semiconductor light emitting device.
- the head lamp 4000 may further include a heat dissipating unit 4012 for dissipating the heat generated from the light source 4001 to the outside and the heat dissipating unit 4012 may include a heat sink 4010, (4011).
- the head lamp 4000 may further include a housing 4009 for holding and supporting the heat dissipating unit 4012 and the reflecting unit 4005.
- the housing 4009 includes a body 4006, And a center hole 4008 for mounting the unit 4012 in a coupled state.
- the housing 4009 may include a front hole 4007 that is integrally connected to the one surface and is bent at a right angle to fix the reflecting portion 4005 on the upper side of the light source 4001.
- the reflective portion 4005 is fixed to the housing 4009 such that the front of the opened portion corresponds to the front hole 4007 and the light reflected through the reflective portion 4005 Can be emitted to the outside through the front hole (4007).
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Abstract
Description
Claims (15)
- 제1 도전형 반도체로 이루어진 베이스층을 제공하는 단계;상기 베이스층 상에 식각정지층이 포함된 마스크를 형성하는 단계;상기 마스크에 상기 베이스층 영역이 노출된 복수의 개구를 형성하는 단계;상기 복수의 개구가 충진되도록 상기 베이스층의 노출된 영역에 제1 도전형 반도체를 성장시킴으로써 복수의 나노 코어를 형성하는 단계;상기 복수의 나노 코어의 측면이 노출되도록 상기 식각정지층을 이용하여 상기 마스크를 부분적으로 제거하는 단계; 및상기 복수의 나노 코어의 표면에 활성층 및 제2 도전형 반도체층을 순차적으로 성장시키는 단계;를 포함하는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 마스크는, 상기 베이스층 상에 형성되며 상기 식각 정지층으로 제공되는 제1 물질층과, 상기 제1 물질층 상에 형성되며 상기 제1 물질층의 식각률보다 낮은 식각률을 갖는 제2 물질층을 포함하는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 마스크는, 상기 베이스층 상에 순차적으로 형성된 제1 내지 제3 물질층을 포함하며,상기 제2 물질층은 상기 제1 및 제3 물질층과 다른 물질로 이루어지고, 상기 식각 정지층으로 제공되는 나노구조 반도체 발광소자 제조방법.
- 제2항에 있어서,상기 제1 및 제3 물질층은 동일한 물질로 이루어지는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 식각정지층에 의한 식각 정지 레벨은 상기 베이스층의 상면으로부터 마스크의 전체 높이의 1/3 지점 이하에 위치하는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 개구의 종횡비는 5:1 이상인 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 복수의 개구를 형성하는 단계와 상기 복수의 나노 코어를 형성하는 단계 사이에, 상기 복수의 개구의 내부 측벽 각각에 상기 마스크와 다른 물질로 이루어진 확산 방지막을 형성하는 단계를 더 포함하는 나노구조 반도체 발광소자 제조방법.
- 제7항에 있어서,상기 확산 방지막을 형성하는 단계는,상기 마스크의 표면에 상기 확산 방지막을 위한 물질막을 형성하는 단계와, 상기 개구의 내부 측벽에만 잔류하도록 상기 물질막 중 상기 마스크의 상면과 상기 베이스층의 노출영역 상에 위치한 부분을 제거하는 단계를 포함하는 나노구조 반도체 발광소자 제조방법.
- 제7항에 있어서,상기 활성층 및 상기 제2 도전형 반도체층을 순차적으로 성장시키는 단계 전에, 상기 나노 코어의 노출된 표면으로부터 상기 확산 방지막을 제거하는 단계를 더 포함하는 나노구조 반도체 발광소자 제조방법.
- 제7항에 있어서,상기 확산 방지막을 제거하는 단계 후에, 상기 확산 방지막 중 상기 식각정지층의 상면 레벨 아래에 위치한 부분이 잔류하는 것을 특징으로 하는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 마스크를 부분적으로 제거하는 단계와, 상기 활성층 및 제2 도전형 반도체층을 순차적으로 성장시키는 단계 사이에, 상기 복수의 나노 코어를 열처리하는 단계를 더 포함하는 나노구조 반도체 발광소자 제조방법.
- 제11항에 있어서,상기 열처리하는 단계는 약 600℃ ∼ 약 1200℃의 온도 범위에서 수행되는 것을 특징으로 하는 나노구조 반도체 발광소자 제조방법.
- 제1항에 있어서,상기 복수의 나노 코어를 형성하는 단계 후에, 상기 복수의 나노 코어 상면이 동일한 레벨로 평탄화되도록 연마공정을 적용하는 단계를 더 포함하는 나노구조 반도체 발광소자 제조방법.
- 제13항에 있어서,상기 복수의 나노 코어의 적어도 일부는 그 직경 및 간격 중 적어도 하나가 다른 나노 코어와 상이한 것을 특징으로 하는 나노구조 반도체 발광소자 제조방법.
- 제1 도전형 반도체로 이루어진 베이스층;상기 베이스층 상에 형성되며, 상기 베이스층 영역이 노출된 복수의 개구를 갖는 마스크;상기 베이스층의 노출된 영역에 각각 형성되며, 제1 도전형 반도체로 이루어진 나노 코어와, 상기 나노 코어의 표면에 순차적으로 형성된 활성층 및 제2 도전형 반도체층을 갖는 복수의 나노 발광구조물; 및상기 나노 코어와 상기 개구의 내부 측벽 사이에 위치하는 확산 방지막을 포함하는 나노구조 반도체 발광소자 제조방법.
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US14/764,349 US9525102B2 (en) | 2013-01-29 | 2014-01-28 | Method for manufacturing nanostructure semiconductor light emitting device |
DE112014000592.4T DE112014000592B4 (de) | 2013-01-29 | 2014-01-28 | Verfahren zum Herstellen von lichtemittierenden Nanostrukturhalbleitervorrichtungen |
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DE112014000592T5 (de) | 2016-02-18 |
US20150372186A1 (en) | 2015-12-24 |
US9379283B2 (en) | 2016-06-28 |
KR20140096980A (ko) | 2014-08-06 |
CN105009309B (zh) | 2017-12-05 |
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