Gas phase enhancement of emission color quality in solid state LEDs
10233390 ยท 2019-03-19
Assignee
Inventors
Cpc classification
Y10S977/774
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L33/28
ELECTRICITY
Y10S977/891
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
H01L33/08
ELECTRICITY
C01P2006/60
CHEMISTRY; METALLURGY
H01L33/30
ELECTRICITY
Y10S977/95
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L33/06
ELECTRICITY
C01P2004/64
CHEMISTRY; METALLURGY
International classification
H01L33/00
ELECTRICITY
H01L33/30
ELECTRICITY
H01L33/06
ELECTRICITY
C09K11/88
CHEMISTRY; METALLURGY
C09K11/02
CHEMISTRY; METALLURGY
H01L33/28
ELECTRICITY
Abstract
Light-emitting materials are made from a porous light-emitting semiconductor having quantum dots (QDs) disposed within the pores. According to some embodiments, the QDs have diameters that are essentially equal in size to the width of the pores. The QDs are formed in the pores by exposing the porous semiconductor to gaseous QD precursor compounds, which react within the pores to yield QDs. According to certain embodiments, the pore size limits the size of the QDs produced by the gas-phase reactions. The QDs absorb light emitted by the light-emitting semiconductor material and reemit light at a longer wavelength than the absorbed light, thereby down-converting light from the semiconductor material.
Claims
1. A method for synthesizing quantum dots (QDs) in a light-emitting semiconductor material, the method comprising: flowing gaseous QD precursors through first pores in a semiconductor material to effect reaction of the QD precursors in the absence of liquid solvent and grow a plurality of first QDs in the first pores having diameters essentially equal to the first pore diameters; and flowing gaseous QD precursors through second pores in a semiconductor material to effect reaction of the QD precursors in the absence of liquid solvent and grow plurality of second QDs in the second pores having diameters essentially equal to the second pore diameters; wherein the second pores have diameters larger than the diameters of the first pores.
2. The method of claim 1, wherein the first pores and the second pores are about 1 nm to about 20 nm in diameter.
3. The method of claim 1, wherein the light-emitting semiconductor material comprises as GaN, AlGaAs, AlGaInP, or AlGaInN, or any derivatives thereof.
4. The method of claim 1, wherein the one or both of the first QDs and the second QDs comprise a semiconductor material selected from CdS, CdSe, ZnS, ZnSe InP, GaP Cd.sub.3P.sub.2 and In.sub.2Se.sub.3.
5. The method of claim 1, wherein the first QDs are green light-emitting QDs.
6. The method of claim 1, wherein the second QDs are red light-emitting QDs.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing summary, as well as the following detailed description, will be better understood when read in conjunction with the appended drawings. For the purpose of illustration only, there is shown in the drawings certain embodiments. It's understood, however, that the inventive concepts disclosed herein are not limited to the precise arrangements and instrumentalities shown in the figures.
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DESCRIPTION
(10) It should be understood that the inventive concepts set forth herein are not limited in their application to the construction details or component arrangements set forth in the following description or illustrated in the drawings. It should also be understood that the phraseology and terminology employed herein are merely for descriptive purposes and should not be considered limiting. It should further be understood that any one of the described features may be used separately or in combination with other features. Other invented systems, methods, features, and advantages will be or become apparent to one with skill in the art upon examining the drawings and the detailed description herein. It is intended that all such additional systems, methods, features, and advantages be protected by the accompanying claims.
(11) The present disclosure generally relates to light emitting devices using a solid-state LED material into which pores have been etched. QDs are synthesized within those pores. When the LED material emits light (i.e., primary light) the QDs absorb some of that light and reemit light having a color determined by the size of the QDs (i.e., secondary light). The light emitted from the light-emitting device therefore includes a combination of the primary and secondary light. Various combinations of LED materials and QD materials and sizes can be used to obtain white light or to obtain other blends of light.
(12) According to some embodiments, the QD materials are synthesized within the pores of the LED material via gas phase reactions. As explained in more detail below, the gas phase QD precursor material diffuse into the pores of the LED material where they react to form QDs. The size of the QDs may be limited by the size of the pores in which the QDs form. In this way, the pores may be thought of as providing a template for QD formation. Since the color of light that a QD emits depends on the size of the QD, the color of emitted light can be tuned by controlling the size of the pores in which the QDs form.
(13) Generally, any solid-state LED semiconductor material can be used. Examples include, but are not restricted to, inorganic solid-state compound semiconductors, such as GaN (blue), AlGaAs (red), AlGaInP (orange-yellow-green), AlGaInN (green-blue), or any derivatives thereof. The characteristic emission colors of each material are provided in parentheses. The examples discussed in this disclosure primarily concern GaN, as it is common to seek to down-convert light from blue-emitting GaN.
(14) Pores can be etched in the solid-state LED semiconductor material using any means known in the art. Examples of controlled etching are contained in Cuong Dang et al., A wavelength engineered emitter incorporating CdSe-based colloidal quantum dots into nanoporous InGaN/GaN multiple quantum well matrix, Phys. Status Solidi, No. 7-8, 2337-339 (2011); Dang et al., A wafer-level integrated white-light-emitting diode incorporating colloidal quantum dots as a nanocomposite luminescent material, Adv. Materials, No. 24, 5915-18 (2012); and Chen et al., High reflectance membrane-based distributed Bragg reflectors for GaN photonics, App. Phys. Lett., No. 101, 221104 (2012). The reader is referred to those references for details concerning the etching of the LED semiconductor material. Generally, the LED semiconductor material is etched using an electrochemical method, for example, anodic etching in an oxalic acid electrolyte. The pore size and concentration can be controlled as a function of the applied voltage. Other methods of etching, such as acid etching and/or inductively coupled plasma-reactive ion (ICP-RI) etching may be used. It is found that the etching technique does not impair the semiconductor material's carrier transport and recombination capability.
(15) In some embodiments, the etching technique produces pores having approximately the same diameter. For example, referring to
(16) Alternatively, the semiconductor material can be selectively etched to include pores of various sizes, as shown in
(17) In other embodiments, as illustrated in
(18) Once the LED semiconductor material is etched to provide pores, QDs are formed within those pores by reacting gas phase QD precursor compounds together within the pores. The precursors may be used to synthesize QDs including, but not restricted to, the following materials: Group II-VI nanoparticles (e.g., CdS, CdSe, ZnS, ZnSe), Group III-V nanoparticles (e.g., InP, GaP), Group II-V nanoparticles (e.g., Cd.sub.3P.sub.2), and Group III-VI nanoparticles (e.g., In.sub.2Se.sub.3). In one embodiment, suitable gas-phase precursors may include, but are not restricted to, a Group II or Group III cation source, (e.g., R.sub.2Cd/Zn; R.sub.3Ga/In (R=organic group)), and a Group V or Group VI anion source, (e.g., H.sub.2S, H.sub.2Se or H.sub.3P). In yet another embodiment, the flow rate of the gas-phase precursors may be controlled using a carrier gas. The carrier gas may include, but is not limited to, an inert gas (e.g., He, N.sub.2 or Ar), or a reducing gas (e.g., H.sub.2).
(19) The pores in the semiconductor material allow the gas phase precursors to diffuse throughout the material. The nucleation and growth of QDs from gaseous precursors may proceed in any pores. Furthermore, since QD stability increases with particle size, under suitable reaction conditions particle growth may continue until all the space is occupied. Therefore, the size of the nanoparticles can be restricted by the pore diameter. By way of example only, QDs having an approximately 5 nm diameter can form in approximately 5 nm pores. In one embodiment, QDs having uniform dimensions can grow in the pores. In another embodiment, QDs having variable diameters grow in the pores. In one embodiment, both red and green QDs grow in the pores of a semiconductor material for a blue-LED (e.g., GaN) at a level that effectively down-converts the LED to produce white light emissions. The resulting material is free of liquid solvents because the QD-producing reactions involve only gas phase precursors.
(20) QDs may be prepared by the reaction of gas phase QD precursors as described in N. L. Pickett et al., in J. Mater. Chem., 1997, 7, 1855 and in J. Mater. Chem., 1996, 6, 507. The size of the resultant QDs may be varied by careful control of the reaction conditions (e.g., temperature, time, etc.), and the addition of pyridine in the gas phase. Likewise, the methods used to synthesize QDs in polymer matrices described by Haggata et al. S. W. Haggata et al., J. Mater. Chem., 1996, 6, 1771 and J. Mater. Chem., 1997, 7, 1996 may be adapted to synthesize QDs in the pores of the LED semiconductor material. The Pickett and Haggata references cited in this paragraph are hereby incorporated by reference in their entirety.
(21) Generally, the gas phase QD precursors are exposed to the pores in parallel or counter flow and allowed to react within the pores. In one embodiment, the pores have variable sizes to accommodate both red and green QD growth. In another embodiment, the reaction conditions are controlled to produce both red and green QDs. In yet another embodiment, the QDs may be formed in the semiconductor material at a level that effectively down-converts the semiconductor material to produce white light emissions.
(22) Gas phase reaction conditions can be used to control QD growth within the semiconductor material. For example, pyridine and higher temperatures may be used to inhibit nanoparticle growth as reported by Pickett et al., Effect of pyridine upon gas-phase reactions between H.sub.2S and Me.sub.2Cd; control of nanoparticle growth, J. Mater. Chem., No. 6, 507-09 (1996). Thus, in one embodiment, the gas-phase synthesis can be carried out in the presence of a Lewis base in the gas phase. For example, the Lewis base can coordinate to the surface of the QDs and control their size. Higher concentrations of a Lewis base can be used to synthesize smaller QDs. Suitable Lewis bases may include, but are not restricted to, pyridine gas. In still another embodiment, the semiconductor may comprise a material that may act as a Lewis base. In another embodiment, the reaction may be carried out at a certain temperature. Suitable temperatures may include, but are not restricted to, approximately 25 C. to 200 C. Higher temperatures can be used to produce smaller QDs. In still another embodiment, a Lewis base concentration and temperature are adjusted during gas-phase synthesis in order to synthesize different size QDs within the semiconductor material. In one embodiment, the Lewis base concentration and temperature can be selectively adjusted to a level that results in synthesis of both red and green QDs within the pores of a semiconductor material for a blue-LED (e.g., GaN) at a level that effectively down-converts the LED to produce white light emissions.
(23) In an alternative embodiment, QDs having same size but different wavelength emissions can be grown within the pores of a semiconductor material. For example, nanoparticle precursors can be selected to grow both Group III-V based QDs (e.g. InP, and including graded dots and alloys) and CdSe QDs. InP QDs emitting at a particular wavelength are relatively smaller than CdSe QDs emitting at the same wavelength. Thus, in an embodiment, InP and CdSe QDs can grow to the same size but emit different wavelengths. In one embodiment, the InP and CdSe QDs grow within pores having uniform diameter, wherein the InP QDs emit red light and the CdSe QDs emit green light. In an embodiment, the concentration of precursors for red-emitting QDs and green-emitting QDs can be selectively adjusted to a level that results in synthesis of both red and green QDs within the pores of a semiconductor material for a blue-LED (e.g., GaN) at a level that effectively down-converts the LED to produce white light emissions.
(24) In one embodiment, a porous semiconductor material 200 is placed in the middle of two streams of gas flowing from opposite directions, 201 and 202, respectively, as illustrated in FIG. 2. The gas streams can include precursors to QDs 204. Referring to
(25) In another embodiment, a porous semiconductor material 300 is placed in the stream of two parallel gas sources 301, 302, as illustrated in
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(27) In the apparatus 500 illustrated in
(28) The particular set-ups illustrated in
(29) The methods and apparatuses described herein can grow QDs within a semiconductor material because gas phase QD precursors can diffuse into nano-size pores and react inside those pores.
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(31) Referring to
(32) The QD precursors can diffuse into the pores and grow to a size that fills the diameter of the pores. In one embodiment, the gaseous precursors include nanoparticle precursors to produce both red 720 and green QDs 730 within the uniform-sized pores. For example, the gas may include precursors for Group III-V based QDs (e.g. InP, and including graded dots and alloys) and CdSe QDs, which will emit different wavelengths at a certain size. In an alternative embodiment, adjusting Lewis base concentration and/or temperature during synthesis can be used to selectively control QD size. In one embodiment, reaction conditions are controlled to grow red-emitting QDs 720 in the bottom half of the semiconductor material, and green-emitting QDs 730 in the top half of the semiconductor material. In yet another embodiment, green and red-emitting QDs are grown within a blue-light emitting semiconductor material having uniform pore diameter at a level that effectively down converts the semiconductor material to white light emissions.
(33) In yet another embodiment, as illustrated in
(34) The present application presents numerous advantages over the prior art. It relies on gaseous precursors, which though larger than individual oxygen and water molecules, are of the same order of magnitude. As illustrated in
(35) It's understood that the above description is intended to be illustrative, and not restrictive. The material has been presented to enable any person skilled in the art to make and use the inventive concepts described herein, and is provided in the context of particular embodiments, variations of which will be readily apparent to those skilled in the art (e.g., some of the disclosed embodiments may be used in combination with each other). Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention therefore should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms including and in which are used as the plain-English equivalents of the respective terms comprising and wherein.
EXAMPLES
Example 1: CdS
(36) CdS QDs may be formed from the gas phase reaction of helium gas streams containing Me.sub.2Cd and H.sub.2S in the presence of pyridine gas. Typical reaction conditions include a He flow rate of 600 cm.sup.3 min.sup.1 and a 30-fold excess of H.sub.2S to Me.sub.2Cd. The particle size may be controlled by varying the pyridine concentration and/or the reaction temperature. Preferably, pyridine:Me.sub.2Cd ratios in the range 1:20 to 2:1, and temperatures between room temperature and 200 C. are employed. It has been found that increasing the pyridine concentration reduces the particle size, while the particle size increases with increasing temperature.
(37) The absorption of the CdS nanoparticles may be tuned from the UV to cyan (bulk band gap 512 nm) depending on the particle size. For example, nanoparticles in the size range 2-20 nm may be expected to emit between approximately 320-500 nm, corresponding with UV to cyan light.
Example 2: CdSe
(38) Reaction conditions similar to those outlined for CdS (above) may be used to synthesize CdSe QDs [N. L. Pickett et al., J. Mater. Chem., 1997, 7, 1855], substituting H.sub.2S for H.sub.2Se. Higher pyridine concentrations may be used to control the particle size (up to 150:1 pyridine:Me.sub.2Cd).
(39) The absorption of the CdSe nanoparticles may be tuned from the blue to the deep red (bulk band gap 717 nm) depending on the particle size. Nanoparticles in the size range 2-20 nm may be expected to emit between approximately 490-700 nm, corresponding with blue to deep red light.
Example 3: ZnS
(40) Reaction conditions similar to those outlined for CdS (above) may be used to synthesize ZnS QDs [N. L. Pickett et al., J. Mater. Chem., 1997, 7, 1855], substituting Me.sub.2Cd for Me.sub.2Zn. Higher reaction temperatures (up to 300 C.) may be advantageous.
(41) The absorption of the ZnS nanoparticles may be tuned across the UV spectrum (bulk band gap 344 nm) depending on the particle size. Nanoparticles in the size range 2-20 nm may be expected to emit between approximately 235-340 nm.
Example 4: ZnSe
(42) Reaction conditions similar to those outlined for ZnS (above) may be used to synthesize ZnSe QDs [N. L. Pickett et al., J. Mater. Chem., 1997, 7, 1855], substituting H.sub.2S for H.sub.2Se. A reducing H.sub.2 carrier gas, rather than inert He, may be more effective at controlling the particle size.
(43) The absorption of the ZnS nanoparticles may be tuned from the UV to the blue (bulk band gap 459 nm) depending on the particle size. Nanoparticles in the size range 2-20 nm may be expected to emit between approximately 295-455 nm, corresponding with UV to indigo light.
Example 5: InP
(44) InP nanoparticles may be synthesized using a reaction procedure similar to those outlined for II-VI QDs (above) from Me.sub.3In and PH.sub.3 gaseous precursors.
(45) The absorption of the InP nanoparticles may be tuned from the green to the near-IR (bulk band gap 925 nm) depending on the particle size. Nanoparticles in the size range 2-20 nm may be expected to emit between approximately 520-875 nm, corresponding with green light to IR radiation.