Phosphor layer for micro-LED applications
11552225 · 2023-01-10
Assignee
Inventors
- Hans-Helmut Bechtel (Roetgen, DE)
- Jens Meyer (Cologne, DE)
- Matthias Heidemann (Alsdorf, DE)
- Petra Huppertz (Roetgen, DE)
- Joerg Feldmann (Aachen, DE)
Cpc classification
H01L27/15
ELECTRICITY
H01L33/504
ELECTRICITY
International classification
Abstract
Embodiments include a device having a micro-LED that includes at least two, individually addressable light emitting diodes on a same substrate; a phosphor converter layer disposed on the micro-LED, the phosphor converter layer including phosphor particles having a D50 of greater than 1 μm and less than 10 μm.
Claims
1. A device comprising: a micro-LED comprising at least two individually addressable light emitting diodes on a same substrate; and a phosphor converter layer disposed on the micro-LED and extending over the at least two light emitting diodes and across a gap therebetween, the phosphor converter layer comprising a plurality of phosphor particles having an average particle size or median diameter (D50) of greater than 1 μm and less than 10 μm, wherein a thickness of the phosphor converter layer is greater than 4 μm and less than 20 μm, wherein the phosphor converter layer further comprises a thin layer of non-luminescent material coating on the phosphor particles, and wherein the thin layer has a thickness of less than 200 nm, the at least two light emitting diodes exhibiting a contrast ratio greater than 1:18, said contrast ratio resulting at least in part from the D50 of the phosphor particles and the thickness of the phosphor converter layer.
2. The device of claim 1, wherein the plurality of phosphor particles has a D50 of greater than 2 μm and less than 7 μm.
3. The device of claim 2, wherein the plurality of phosphor particles has a D50 of greater than 3 μm and less than 5 μm.
4. The device of claim 1, wherein the thickness of the phosphor converter layer is greater than 8 μm and less than 15 μm.
5. The device of claim 1, wherein the thickness of the phosphor converter layer is greater than 10 μm and less than 13 μm.
6. The device of claim 1, wherein the phosphor converter layer further comprises a matrix, and the matrix has a refractive index of 1 or greater and less than or equal to 1.5.
7. The device of claim 6, wherein the matrix has a refractive index of 1 or greater and less than 1.4.
8. The device of claim 7, wherein the matrix has a refractive index of 1 or greater and less than 1.2.
9. The device of claim 1, wherein the thin layer comprises a metal oxide.
10. The device of claim 9, wherein the thin layer comprises at least one of Al.sub.2O.sub.3, HfO.sub.2, Ta.sub.2O.sub.5, ZrO.sub.2, TiO.sub.2, and SiO.sub.2.
11. The device of claim 1, wherein the thin layer has a thickness between 40-150 nm.
12. The device of claim 1, the contrast ratio being greater than 1:100.
13. A method for making the device of claim 1, the method comprising: depositing the plurality of phosphor particles in a layer that extends over the at least two light emitting diodes on the substrate and across the gap between the at least two light emitting diodes; and forming the thin layer of non-luminescent material so as to coat the phosphor particles.
14. The method of claim 13, wherein the phosphor converter layer is deposited by spray coating or sedimentation.
15. The method of claim 13, wherein the thin layer is formed by atomic layer deposition.
16. The method of claim 13, wherein the thin layer comprises a metal oxide.
17. The method of claim 16, wherein the thin layer comprises at least one of Al.sub.2O.sub.3, HfO.sub.2, Ta.sub.2O.sub.5, ZrO.sub.2, TiO.sub.2, and SiO.sub.2.
18. The method of claim 13, wherein the plurality of phosphor particles has a D50 of greater than 2 μm and less than 7 μm.
19. The method of claim 13, wherein the thickness of the phosphor converter layer is greater than 8 μm and less than 15 μm.
20. The method of claim 13, wherein the phosphor converter layer further comprises a matrix, and the matrix has a refractive index of 1 or greater and less than or equal to 1.5.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(16) Micro-LEDs, also referred to as μLEDs, are arrays of a large number of individually addressable LED devices on one chip. Micro-LED arrays have application in lighting, for instance automotive lighting, and displays. As the individual LEDs, or pixels, are individually addressable, light patterns can be displayed on the micro-LED.
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(18) One method for forming a micro-LED is to use epitaxial growth to form the multiple individual LEDs 110 on a die in a flip-chip construction as is known in the art.
(19) A phosphor converter 163 is on LED dies 110. The phosphor converter 163 may be formed of phosphor particles contained in a matrix, for example, garnet particles contained in silicone. Alternatively, or in addition, the phosphor converter 163 contains a densely sintered phosphor ceramic, such as Lumiramic™. In one example, the individual LEDs produce a blue light and the phosphor converter converts the blue light to a white light to produce a micro-LED that is monochrome white at a CCT of about 5700K.
(20) The phosphor converter 163 can be defined by three parameters: (a) its thickness, (b) the refractive index of the matrix, and (c) the particle size and the refractive index of the phosphor material. The thickness, or width, of phosphor converter 163 is represented by W in
(21) A problem encountered with micro-LEDs is that there can be very low optical contrast between neighboring pixels when one pixel is on and a neighboring pixel is off. Thus, for instance, if the pixels in row 120 of
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(24) To increase the contrast between on state pixels and off state pixels, and hence improve the optical resolution, parameters that define the phosphor converter 163 were modified.
(25) Lowering the refractive index of the matrix for the phosphor converter 163 increases scattering and thus the optical contrast.
(26) Reducing the particle size of the phosphor material in the phosphor converter 163 and reducing the thickness W of the phosphor converter 163 also increases the optical contrast.
(27) Thus a phosphor converter with a high optical contrast (above 300) can only be realized with phosphor particles size D50 of less than 5 μm and a thickness W well below 15 μm when the refractive index is=1. An optical contrast ratio of better than 1:100 can be achieved with refractive index of=1 when the particle size is less than 9 μm and the thickness is less than 15 μm. In practice, D50 of phosphor material particles is limited to 1-3 μm, with the quantum efficiency decreasing with decreasing particles size of the phosphor. Also, the overall layer thickness is limited by the maximum tolerable activator concentration of the phosphor materials (increases may also result in quantum efficiency decreases). With a phosphor converter layer matrix material (like silicone) the parameter space for a high contrast layer is extremely limited. On the other hand, the matrix material within the phosphor converter has two functions. First, to provide mechanical stability to the phosphor converter layer, and secondly, to enhance the blue light extraction from the underlying LED die.
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(29) Next, as shown in
(30) The resulting phosphor converter 663 includes a thin layer of phosphor particles 630 covered with a thin layer 660 of non-luminescent material, such as Al.sub.2O.sub.3. The thickness W of the phosphor converter 663 is less than 15 μm.
(31) In addition to having a high optical contrast, the phosphor converter 663 is mechanically stable, and enhances extraction of light from the LED die, by coupling phosphor particles which touch the LED surface optically, without significantly decreasing light scattering in the layer. The phosphor converter 663 also has high reliability necessary for a variety of application, including, for example, automotive forward lighting standards. Furthermore, such a phosphor converter layer may be used on any LED, not just micro-LED, where it may provide advantages of reliability and enhancing light extraction.
(32) ALD Details:
(33) Atomic Layer Deposition (ALD) is used to deposit the thin layer 660 on the optical converter 663. ALD is a chemical vapor deposition process which allows the deposition of thin layers of material by applying one atomic layer of a material per cycle in a controllable way. In such process a polymeric network is formed by reaction of a metal oxide precursor with an oxygen source such as water and/or ozone in the gas phase. The ALD reaction is split in (at least) two parts. In a first step the metal (oxide) precursor is fed into the reactor and adsorbs and/or reacts with reactive groups on the surfaces and substantially all non-reacted or adsorbed precursor molecules are removed by reactor purging. In a second step the oxygen source is fed into the reactor and reacts with the metal source on the particle surfaces followed by purging of the reactor to remove substantially all remaining oxygen source molecules and hydrolysis products formed by condensation reactions. The two steps lead to formation of an atomic layer (or monolayer) because of the self-limiting nature of the surface reaction. These atomic layer reaction steps are repeated multiple times to form the final ALD coating. The term metal oxide precursor especially indicates a precursor of the metal oxide. The precursor itself may not be a metal oxide, but may e.g. include metal organic molecule. Hence, especially the metal (oxide) precursors for ALD may typically include metal halides, alkoxides, amides, and other metal (organic) compounds.
(34) The step by step nature of the ALD process allows conformal coatings also on and in structures with large aspect-ratio such as phosphor particles. The ALD process further allows it to deposit layers of different composition by consecutively feeding different metal oxide precursor into the reactor to form multicomponent layers or nanolaminates with tailored optical properties.
(35) Hence, in a specific embodiment an ALD layer is applied on a GaN surface with phosphor particles to mechanically and optically bond the particles to the substrate. The process is set such that a layer connects particles with the substrate and particle with their neighboring particle. Thus, a phosphor particle network with modified optical properties is formed on the GaN surface enhancing the light output of the LED. The ALD layer may typically have a layer thickness in the 20-500 nm, especially 50-200 nm range.
(36) In a further embodiment the ALD process is set such that not only conformal deposition occurs but also CVD-like growth leading to thicker layers in the voids in between the phosphor particles. CDV-like growth can be realized by shorten the purge time between pulses or reducing the reactor temperature.
(37) A (non-limiting) number of suitable materials for the ALD second coating layer are listed in the following table 1:
(38) TABLE-US-00001 TABLE 1 Oxide Oxygen Deposition material Metal (oxide_precursor source T [° C.] Al.sub.2O.sub.3 Al(CH.sub.3).sub.3 (TMA) or HAl(CH.sub.3).sub.2 H.sub.2O or O.sub.3 100-400 HfO.sub.2 Hf(N(CH.sub.3).sub.2).sub.4 or Hf(N(CH.sub.2CH.sub.3).sub.2).sub.4 H.sub.2O 80-300 Ta.sub.2O.sub.5 TaCl.sub.5 or Ta(N(CH.sub.3).sub.2).sub.5 H.sub.2O 80-300 ZrO.sub.2 ZrCl.sub.4 or Zr(N(CH.sub.3).sub.2).sub.4 H.sub.2O 80-300 TiO.sub.2 TiCl.sub.4, Ti(OCH.sub.3).sub.4 or Ti(OEt).sub.4 H.sub.2O 80-300 SiO.sub.2 SiCl.sub.4, H.sub.2N(CH.sub.2).sub.3Si(OEt).sub.3 or Si(OEt).sub.4 H.sub.2O or O.sub.3 150-300
(39) Alternatively or additionally, niobium oxide (especially Nb.sub.2O.sub.5) or yttrium oxide (Y.sub.2O.sub.3) may be applied. Metal precursors thereof are e.g., tert-butylimido)-tris (diethylamino)-niobium, NbF.sub.5, or NbCl.sub.5, and Tris(ethylcyclopentadienyl) Yttrium, respectively.
(40) However, other materials may also be applied. Hence, in the atomic layer deposition process a metal oxide precursor may especially be selected from the group of metal oxide precursors of metals selected from the group consisting of Al, Hf, Ta, Zr, Ti and Si. Alternatively or additionally, one or more of Ga, Ge, V and Nb may be applied. Even more especially, alternating layers of two or more of these precursors are applied, wherein at least one precursor is selected from the group consisting of an Al metal oxide precursor and an Si metal oxide precursor, especially an Al metal oxide metal oxide precursor, and another precursor is selected from the group consisting of a Hf metal oxide precursor, a Ta metal oxide precursor, a Zr metal oxide precursor and a Ti metal oxide precursor, especially selected from the group consisting of a Hf metal oxide precursor, a Ta metal oxide precursor, and a Zr metal oxide precursor, even more especially a Ta metal oxide precursor. Especially Hf, Zr, and Ta appear to provide relatively light transmissive layers, whereas Ti, for instance, may provide relatively less light transmissive layers. Processing with Ta, Hf and Zr seems to be relatively easier than Si, for instance. The terms “oxide precursor” or “metal oxide precursor” or “metal (oxide) precursor” may also refer to a combination of two or more chemically different precursors. These precursors especially form an oxide upon reaction with the oxygen source (and are therefore indicated as metal oxide precursor).
EXAMPLE
(41) To form a phosphor converter layer on an LED in accordance with the embodiments disclosed herein, a NYAG4454 (Intematix corp.) phosphor particle material with D50=3.8 μm was used. The phosphor particles were sedimented in ethanol with a screen weight of 2.5 mg/cm.sup.2 on a blue thin film flip-chip (TFFC) LED. Once the phosphor particles had been applied to the LED, an Al.sub.2O.sub.3 coating was then applied in a Picosun Oy ALD reactor. Precursor materials were trimethylaluminum and H.sub.2O for 0, to make the Al.sub.2O.sub.3 film. The deposition temperature was set to 150° C. The pulse time in which precursor was introduced was 100 ms, followed by a purge with nitrogen gas of 30 seconds, followed by a pulse of gas-phase water for 100 ms, followed by another purge of nitrogen gas for 30 seconds. Time was allowed after the pulse for the all of the precursor to react with the particles, and LED.
(42) The ALD cycle was repeated to form Al.sub.2O.sub.3 inorganic coating layers in 20 nm steps. At each 20 nm step, the emitted flux from the LED at IA was measured in an integrating sphere.
(43) The optical contrast of the example phosphor converter was also measured.
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(47) The following enumerated clauses provide additional non-limiting aspects of the disclosure.
(48) Clause 1. A device comprising: a micro-LED comprising at least two individually addressable light emitting diodes on a same substrate; and a phosphor converter layer disposed on the micro-LED, the phosphor converter layer comprising a plurality of phosphor particles having a D50 of greater than 1 μm and less than 10 μm, wherein a thickness of the phosphor converter layer is greater than 4 μm and less than 20 μm, wherein the phosphor converter layer further comprises a thin layer of non-luminescent material coating on the phosphor particles, and wherein the thin layer has a thickness of less than 200 nm.
(49) Clause 2. The device of clause 1, wherein the plurality of phosphor particles has a D50 of greater than 2 μm and less than 7 μm.
(50) Clause 3. The device of clause 2, wherein the plurality of phosphor particles has a D50 of greater than 3 μm and less than 5 μm.
(51) Clause 4. The device according to any one of the preceding clauses, wherein the particle size D50 is less than 9 μm and the thickness of the thin layer is less than 15 μm.
(52) Clause 5. The device of clause 4, wherein a thickness of the phosphor converter layer is greater than 8 μm and less than 15 μm.
(53) Clause 6. The device of clause 5, wherein a thickness of the phosphor converter layer is greater than 10 μm and less than 13 μm.
(54) Clause 7. The device of any of clauses 1-6, wherein the phosphor converter layer further comprises a matrix, and the matrix has a refractive index of 1 or greater and less than or equal to 1.5.
(55) Clause 8. The device of clause 7, wherein the matrix has a refractive index of 1 or greater and less than 1.4.
(56) Clause 9. The device of clause 8, wherein the matrix has a refractive index of 1 or greater and less than 1.2.
(57) Clause 10. The device of any of clauses 1-9, wherein the phosphor converter layer is obtainable by spray coating or sedimentation.
(58) Clause 11. The device of clause 10, wherein the thin layer comprises a metal oxide.
(59) Clause 12. The device of clause 11, wherein the thin layer comprises at least one of Al.sub.2O.sub.3, HfO.sub.2, Ta.sub.2O.sub.5, ZrO.sub.2, TiO.sub.2, and SiO.sub.3.
(60) Clause 13. The device of clause 10, wherein the thin layer is formed by atomic layer deposition.
(61) Clause 14. The device of clause 10, wherein the thin layer has a thickness between 40-150 nm.
(62) Clause 15. A device comprising: a light emitting diode; and a phosphor converter layer on the light emitting diode, the phosphor converter layer including a plurality of phosphor particles and a thin layer of a non-luminescent material formed over the phosphor particles, wherein a thickness of the phosphor converter layer is greater than 4 μm and less than 20 μm, wherein the phosphor converter layer further comprises a thin layer of non-luminescent material coating on the phosphor particles, and wherein the thin layer has a thickness of less than 200 nm.
(63) This disclosure is illustrative and not limiting. Further modifications will be apparent to one skilled in the art in light of this disclosure and are intended to fall within the scope of the appended claims.