Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
  • H01L33/50—Wavelength conversion elements
  • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
  • H01L33/502—Wavelength conversion materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/77342—Silicates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
  • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
  • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
  • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
  • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
  • H01L2224/321—Disposition
  • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
  • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
  • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
  • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
  • H01L2224/42—Wire connectors; Manufacturing methods related thereto
  • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
  • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
  • H01L2224/4805—Shape
  • H01L2224/4809—Loop shape
  • H01L2224/48091—Arched
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
  • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
  • H01L2224/42—Wire connectors; Manufacturing methods related thereto
  • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
  • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
  • H01L2224/481—Disposition
  • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
  • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
  • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
  • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
  • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
  • H01L2224/732—Location after the connecting process
  • H01L2224/73251—Location after the connecting process on different surfaces
  • H01L2224/73265—Layer and wire connectors

Definitions

• the invention is based on an LED with a low color temperature.
• a color temperature in the range of about 2000 to 6000 K, preferably up to 5000 K, ver ⁇ stood.
• Simple LEDs which have set themselves the goal of warm white light colors, are based on UV chips. Due to the large energy difference between the UV range and the short-wave visible range (blue) and the UV-related, due to the higher energy, radiation-related faster aging of the housing and the phosphor coating these LEDs reach neither the life nor the efficiency of neutral white LEDs, as they are currently available on the basis of blue-emitting chips.
• RGB LEDs based on luminescence conversion LEDs with sulfide and thiogallate phosphors, see for example WO 01/24229.
• the phosphors proposed therein do not meet the requirements with regard to long-term stability and efficiency when using high-performance chips which achieve a high operating temperature.
• the sulfides are chemically unstable to moisture and the thiogallates proposed therein show pronounced temperature quenching.
• the decompose known sulfide phosphors also to form toxic gases such as hydrogen sulfide.
• Another task is the simultaneous generation of highest possible efficiency with high stability.
• a light-emitting diode based on InGaN or InGaAIP or a discharge lamp based on low pressure or high pressure or an electroluminescent lamp is particularly suitable for the light source as the primary radiation source.
• These include, in particular, fluorescent lamps or compact fluorescent lamps as well as high-pressure mercury lamps which are improved in terms of color.
• this phosphor can be efficiently excited by a whole series of light sources, including LEDs (for example of the type InGaN), the UV or blue. emit as primary radiation.
• lamps in particular Hg low-pressure and high-pressure lamps, as well as UV and VUV radiators see between about 140 and 480 nm, for example excimer radiators. At 160 nm, quantum efficiency is still around 50%.
• he load for Indium ⁇ based discharge lamps use, so low-pressure or Hochdruckentla ⁇ Dungslampen whose essential filling ingredient is indium halide.
• the LED is embodied as a white emitting luminescence conversion LED, consisting of a primary radiation source, which is a chip which emits in the blue spectral range, in particular 430 to 490 nm, preferably 445 to 470 nm. This avoids the UV radiation which is detrimental to the lifetime.
• This luminescent material is also particularly suitable for applications with full-color luminescence conversion LEDs as well as luminescence conversion LEDs with arbitrarily adjustable colors based on a UV blue primary emitting LED.
• the first luminescent substance consists of the class of chlorosilicates. It is in particular calcium-magnesium chlorosilicate (Ca 8 Mg (Si0 4 ) 4 Cl 2 ) as a green to yellow emitting phosphor.
• the known per se chlorosilicate skeleton with europium (Eu), and possibly additionally with manganese (Mn) doped.
• This phosphor is chosen so that it emits green with a peak wavelength in the range 500 to 520 nm, in particular 505 to 515 nm. In principle, such phosphors are known from DE 100 26 435 and DE-GM 201 08 013.
• Other suitable chlorosilicates are described for example in CN-A 1 1 86 103.
• the second phosphor is a nitridosilicate of the general formula (Ca, Sr) 2 Si 5 N 8 : Eu, whereby a color temperature of at most 5000 K is achieved. But even higher color temperatures up to 6000 K can be achieved with it. This is done in particular by an increase in the chloroformate-nitridosilicate mixing ratio, for example, instead of 1.5, significantly more, in particular 2.5 to 4, and a reduction in the total phosphor concentration in the resin or Silicone But also the use of Nitndosilikaten the basic form MS ⁇ 7N10 is possible
• this phosphor combination of a blue-emitting LED, especially of the InGaN type, can be efficiently excited
• the stable, relatively short-wave emitting green phosphor Chlorosi hkat with peak wavelength of about 511 nm it is possible to dispense with a deep red phosphor, such as high strontium-containing Nit ⁇ dosilikat
• a deep red phosphor such as high strontium-containing Nit ⁇ dosilikat
• the orange-red phosphor used according to the invention Ca nitnosilicate Eu which at most contains small amounts of Sr, is advantageously designed so that it absorbs at least the short-wave component of the green color of the phosphor used, and in particular it absorbs this component more strongly than the long-wave component. Such absorptions are normally avoided as far as possible However, it advantageously takes advantage of this effect.
• the second phosphor component is the nitro silicate of the type mentioned at the outset (Sr 3 Ca 1 a ) 2Si 5 N 8 Eu in a suitable composition.
• a 0 to 0.15 is particularly preferred. 0 ⁇ a ⁇ 0.1
• LEDs with a color rendering index Ra of up to 95 provide a typical Ra value, depending on the desired optimization at 88 to 95.
• further phosphors can be added to improve the color reproduction, for example YAG Ce, ( Lu, Y) 3 (Al, Ga) 5 O 12 Ce, (Sr, Ba, Ca) S 12 O 2 N 2 Eu or also (Sr 1 Ba, Ca) 2SiO4: Eu. These emit in the yellow-green range with peak emission at 530 to 570 nm.
• a further particular advantage is that targeted self-absorption makes it possible to use two types of phosphors which show particularly high stability in an LED, but which, at first glance, do not appear compatible with one another in order to achieve this goal. Only a specific careful coordination of the two phosphors shows the desired effect in order to be able to realize color rendering values over 90.
• Applicable mixing ratios are usually usually between 1: 9 and 9: 1, depending on the desired result, ie in particular color temperature and color location.
• a low color temperature LED designed as a white emitting luminescence conversion LED, having a primary radiation source, which is a chip emitting in the blue spectral region, and a layer of two phosphors connected in front, both of which partially emit the radiation of the chip wherein the first phosphor originates from the class of green-emitting chlorosilicates with a doping of europium and possibly additionally manganese, the empirical formula Ca8-x-yEu ⁇ Mn y Mg (SiO.sub.4) .sub.4Cl.sub.2 being ## STR5 ## where x.gtoreq.0.005 and 0 ⁇ y ⁇ 1, and that the second phosphor is an orange-red Nitridosili ⁇ kat of formula (Ca 1 a Sr a.) 2 Si 5 N 8: Eu, with 0 ⁇ a ⁇ 0.15, wherein the proportions of so- ⁇ be mixed that a color temperature of at most 6000 K, in
• Mn allows the determination of the average emission wavelength.
• the chip is an InGaN chip, as these show high efficiency.
• a color temperature down to 2000 K, in particular 2700 to 3300 K can be achieved with such an LED structure with high stability.
• high color rendering indices in the range of 87 to 95 can be achieved under stable, steady state operation.
• an essential need for the use of white LEDs in general illumination is satisfied.
• the emission of the chip is preferably such that it has a peak wavelength in the range of 445 to 465 nm, in particular 450 to 455 nm.
• the highest efficiencies of the primary radiation can be achieved.
• Particularly suitable is a chlorosilicate having an emission in the range 500 to 520 nm as the peak wavelength.
• This original property acts as an effective emission in the LED, typically shifted by 5 to 20 nm towards longer wavelengths.
• the width of the emission changes.
• a typical original FWHM (fill width half maximum) is 60 nm, which typically widens to 70 to 80 nm in the LED.
• a nitridosilicate whose emission has a peak wavelength in the range 600 to 620 nm, in particular 605 to 615 nm.
• the best color rendering values can be achieved if the following direction is taken into account, namely that the absorption behavior of the nitridosilicate within the original FWHM of the emission of the chlorosilicate exhibits a gradient, the value at the short-wave edge being higher than the corresponding value at the long-wave edge, for example by at least a factor of two to three.
• the invention further relates to an illumination system with LEDs as described above, wherein the illumination system also contains electronic components. These convey, for example, the dimmability.
• Another task of the electronics is the control of individual LEDs or groups of LEDs. These functions can be realized by previously known electronic elements.
• FIG. 1 shows the underlying mechanism of the invention
• FIG. 2 shows the emission spectrum of various LEDs according to the invention
• Figure 3 shows the structure of an LED
• FIG. 4 shows the emission spectrum of an LED as a function of the operating time
• FIG. 5 shows the decrease in brightness of an LED as a function of the operating time
• FIG. 6 shows the shift of the y-coordinate of an LED as a function of the operating duration
• FIG. 7 shows the emission spectrum of a LED according to the prior art as a function of the operating time
• FIG. 8 shows the displacement of the y-coordinate of an LED according to the state of FIG
• FIG. 9 shows the position of the color locus of different white LEDs
• FIG. 10 shows a lighting system based on warm white LEDs.
• FIG. 11 shows a low-pressure lamp with indium filling using suitable phosphors.
• FIG. It shows the emission of the phosphor Ca 8 .
• the emission maximum of the pure phosphor is 511 nm.
• the excitation was carried out at 460 nm.
• the FWHM is 76 nm.
• the course of absorption of the nitridosilicate is crucial, which has a strong gradient in the FWHM of the chlorosilicate. What is essential here is the course between the shortwave edge of the FWHM ( ⁇ 1) and the longwave edge of the FWHM ( ⁇ 2), in each case based on the chlorosilicate.
• the absorption increases greatly to longer Wellen ⁇ lengths.
• the effect of the chlorosilicate in the LED shifts to longer wavelength n, see the dashed line whose maximum is now shifted by about 15 nm.
• Figure 2 shows the emission spectrum of various LEDs designed for different color temperatures.
• the range of color temperatures ranges from wa 2800 K to more than 4000 K.
• the following combinations were used for the five color temperatures:
• the construction of a light source for white light is shown explicitly in FIG.
• the light source is a semiconductor device with a chip 1 of the type InGaN with a peak emission wavelength of 440 to 470 nm, for example 455 nm, which is embedded in an opaque base housing 8 in the region of a recess 9.
• the chip 1 is connected via a bonding wire 14 to a first terminal 3 and directly to a second electrical terminal 2.
• the recess 9 is filled with a potting compound 5 containing as main components a resin (or silicone) (80 to 90 wt .-%) and phosphor pigments 6 from a mixture of two phosphors (less than 20 wt .-%).
• a first phosphor is the chlorosilicate presented as the first embodiment with 2.5% Eu
• the second is an orange-red emitting phosphor, here in particular Ca 2 Si 5 N 8 : Eu (2%).
• the recess 9 has a wall 17, which serves as a reflector for the primary and secondary radiation from the chip 1 and the pigments 6. The combination of blue primary and green or red secondary radiation mixes to warm white with high Ra from 87 to 95 and color temperatures as shown in the above table.
• the nitridosilicate contains M a Si y N z : Eu as a permanent component Ca and as an admixture Sr in a proportion of 0 to 15 mol%.
• the efficiency and the color rendering index Ra are adjusted by the level of doping with Eu, preferably a value for Eu of 1 to 4 mol% of the M. It has been found that to achieve high color rendering indices, a small addition of Sr ( ⁇ 10
• M Preferably in the range from 0.5 to 15 mol% of M (preferably from 1 to 4 mol%).
• the emission spectrum of a typical embodiment as a function of the lifetime is shown in FIG. It shows the intensity in arbitrary units as a function of wavelength (in nm).
• the peaks of the primary radiation at 460 nm, the chlorosilicate at about 530 nm and the nitridosilicate at about 610 nm can be clearly seen. It shows a high constancy after 1000 hours. This applies to both the Ra (constant 93) and the color temperature (3550 K + - 10 K).
• FIG. 5 shows the decrease in brightness of various LEDs according to the invention from Table 1 over 1000 hours of operation at 85 ° C. and 85% relative humidity. Humidity. The decrease is in the order of a few percent and is thus considerably better than previously known white LEDs with similar high color rendering.
• the y color coordinate of various LEDs according to the invention from Table 1 is over 1000 hours of operation at 85 ° C. and 85% relative humidity. Humidity shows ge. There is practically no drift.
• FIG. 9 shows the wide range of color temperatures achievable with the LED according to the invention, as described in Table 1.
• FIG. 10 shows a lighting system 5, in which, in addition to the LEDs 6 according to the invention, the control electronics 7 are also accommodated in a housing 8. With a cover 9 is designated.
• FIG. 11 shows a low-pressure discharge lamp 20 with a mercury-free gas filling 21 (schematized) which contains an indium compound and a buffer gas analogously to WO 02/10374, wherein a layer 22 made of a phosphor mixture is mounted on the inside of the piston 23.
• a first phosphor is the chlorosilicate with 2.5% Eu introduced as the first embodiment, the second is an orange-red emitting phosphor, here in particular Ca 2 Si 5 N 8 : Eu (2%).
• this phosphor mixture is ideally adapted to the indium radiation because it has substantial proportions both in the UV and in the blue spectral range, which are both equally well absorbed by this mixture, what makes them superior in this use against the previously known phosphors.
• These known phosphors appreciably absorb either only the UV radiation or the blue radiation of the indium, so that the indium lamp according to the invention shows a significantly higher efficiency.
• This statement also applies to a high-pressure indium lamp as known per se from US Pat. No. 4,810,938.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
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• Manufacturing & Machinery (AREA)
• Computer Hardware Design (AREA)
• Power Engineering (AREA)
• Luminescent Compositions (AREA)
• Vessels And Coating Films For Discharge Lamps (AREA)

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• 2004
  • 2004-08-05 DE DE102004038199A patent/DE102004038199A1/de not_active Withdrawn
• 2005
  • 2005-07-15 US US11/659,604 patent/US8979318B2/en not_active Expired - Fee Related
  • 2005-07-15 WO PCT/DE2005/001252 patent/WO2006012833A2/de active Application Filing
  • 2005-07-15 CN CN200580026365.0A patent/CN1993838B/zh not_active Expired - Fee Related
  • 2005-07-15 KR KR1020067026276A patent/KR101247232B1/ko active IP Right Grant
  • 2005-07-15 EP EP05782756A patent/EP1774600A2/de not_active Withdrawn
  • 2005-07-15 JP JP2007524165A patent/JP4587330B2/ja not_active Expired - Fee Related
  • 2005-08-03 TW TW094126329A patent/TWI389333B/zh not_active IP Right Cessation

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