Classifications

• • 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
  • C09K11/7734—Aluminates
• • 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
  • C09K11/0883—Arsenides; Nitrides; Phosphides
• • 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
  • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission
  • H01L27/153—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission in a repetitive configuration, e.g. LED bars
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S5/00—Semiconductor lasers
  • H01S5/06—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium
  • H01S5/0607—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium by varying physical parameters other than the potential of the electrodes, e.g. by an electric or magnetic field, mechanical deformation, pressure, light, temperature
  • H01S5/0608—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium by varying physical parameters other than the potential of the electrodes, e.g. by an electric or magnetic field, mechanical deformation, pressure, light, temperature controlled by light, e.g. optical switch
  • H01S5/0609—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium by varying physical parameters other than the potential of the electrodes, e.g. by an electric or magnetic field, mechanical deformation, pressure, light, temperature controlled by light, e.g. optical switch acting on an absorbing region, e.g. wavelength convertors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/85—Arrangements for extracting light from the devices

Definitions

• the present invention relates to novel phosphor mixtures and a light emitting device, in particular a light emitting device with phosphor conversion, such as a pc-LED (phosphor conversion light emitting device) containing at least one novel phosphor mixture.
• a light emitting device with phosphor conversion such as a pc-LED (phosphor conversion light emitting device) containing at least one novel phosphor mixture.
• the phosphor mixtures can be used in phosphor-converted LEDs with a semiconductor emitting in the violet spectral region.
• the present invention relates to a lighting system, which may include the light-emitting devices of the invention, as well as a
• the present invention additionally relates to a process for the preparation of the phosphor mixtures according to the invention and to their use in light-emitting devices, in particular in US Pat
• LEDs Light-emitting diodes
• LEDs for use in general lighting and / or in special lighting, for the conversion of blue, violet and / or
• the phosphor mixtures according to the invention are particularly suitable for use in dynamic lighting systems for generating white or colored light spectra with special properties, such as different levels of activation of melatonin synthesis in the human body in white light spectra or dynamic adaptation to different levels of chlorophyll absorption Special lighting systems for the
• US 2004/0105264 A1 relates to a method and apparatus having a multiple light source illumination device, the design and construction of which are derived from the lighting requirements of the specific application.
• the resulting illumination device allows illumination in accordance with the principles of proper lighting practice for optimum performance of visual tasks in the most efficient and cost effective manner.
• the coupling with sensors and logic control allows the illumination intensity and spectrum to be changed according to the changing needs of the user.
• Light is selected depending on a given time scheme.
• WO 2012/033750 AI relates to light emitting diode (LED) light sources and
• LED Light emitting diode
• at least one LED source is configured to deliver an associated light output having an associated color of each of a plurality of colors; and a controller for selectively powering the LED sources for generating an alternating pattern of the associated light outputs and a corresponding alternating pattern of light is configured, which is delivered with the multiple colors and is visible to an observer.
• Lighting method provided with which a biologically optimized lighting situation can be produced in a local area, which is characterized by at least one specific characteristic.
• LEDs as light sources in lighting systems allows the principle unrestricted ability to combine the most diverse basic spectra together in one luminaire in order to realize dynamically adapted light spectra over time. Due to the laws of additive color mixing, for example, solid-color emitting semiconductor LEDs, which do not generate light
• Example the meaningful combination of 4 separate light sources allow.
• corresponding supply lines must be provided in the lighting system for the individual channels, which in turn can have a negative effect on the minimum required installation space.
• Phosphor conversion is based on a blue-emitting semiconductor diode whose blue high-energy light in a phosphor layer containing fluorescent phosphors, partially absorbed and in light of lower energy or
• phosphors that emit green, yellow, orange and / or red light.
• the combination of these phosphors in the right proportions results in interaction with the unabsorbed residual blue light, the ability to create tailored light spectra with respect to the color location of the emitted light.
• the color location of the light emitted from the overall system can be adjusted within certain limits.
• Phosphors such as nitride-based systems see. WHERE
• the red phosphor absorbs parts of the from the green phosphor emitted light due to the said excitability in the green region of the light spectrum.
• a similar problem arises when combining a violet-emitting semiconductor diode with a blue-emitting phosphor excited by the violet light and a green-emitting phosphor which is additionally excited by the blue light of the blue emitting phosphor. Again, the green phosphor absorbs parts of the blue light of the blue phosphor.
• Semiconductor emitted light is in this case an integral part of the light emitted from the phosphor converted LED light, without which would set a different color location. Due to the spectral emission profiles of the semiconductor and the
• the spectral overall profile in addition to the unique color location and the spectral overall profile of the light emitted from the phosphor converted LED light is uniquely determined.
• the spectral overall profile in turn determines other characteristics of the emitted light, such. For example, the color rendering index. Due to the uniqueness of the color location and the related
• the object of the present invention is to provide phosphor mixtures which are used in a light-emitting device, preferably a phosphor-converted LED, which is equipped with a semiconductor emitting in the violet and / or ultraviolet spectral range, and which provides the flexibility and overall efficiency of the energy conversion
• a further object of the invention is to provide phosphor mixtures which make it possible to produce various light-emitting devices, preferably LEDs, having the same color locus, color rendering index and / or same correlated color temperature, but differing in their spectral profiles and the particular characteristics associated therewith
• the amount of the difference in the x color coordinates of the color locations to be compared of the different light emitting devices in the CIE-1931 standard (2 ° standard observer) standard is ⁇ 0.007; this also applies to the amount of the difference of the y color coordinates (valid in the same color system) of the color locus to be compared;
• Devices at ⁇ 10%, preferably at ⁇ 7%, more preferably at ⁇ 5%.
• Particular properties which are coupled to the spectral profile are, for example, the proportion and intensity of individual colors or color ranges in the spectrum.
• light with different levels of blue is used in dynamic lighting systems for "human centric lighting” applications, where the biological light effect on humans is the focus of the lighting concept , which take into account different levels of chlorophyll absorption, can be used.
• the present invention aims to provide such dynamic
• Lighting systems which are suitable for example for “human centric lighting” applications or for plant breeding.
• corresponding illumination system to provide a method for producing the phosphor mixtures according to the invention and their use in a light-emitting device for light conversion.
• phosphor mixtures which contain at least one phosphor which can be emitted in the green spectral range of visible light and excited in the violet and / or ultraviolet spectral range, and contain at least one further phosphor which is present either in the can be emitted in the blue spectral range of visible light and excited in the violet and / or ultraviolet spectral range, emitted in the cyan spectral range of visible light and excited in the blue, violet and / or ultraviolet spectral range, emitted orange spectral range of visible light and blue, violet and / or ultraviolet spectral range can be excited or emitted in the red spectral range of visible light and excited in the blue, violet and / or ultraviolet spectral range.
• the inventors of the present invention have surprisingly found that the phosphor mixtures according to the invention are suitable for use as conversion material in light-emitting devices, in particular in LEDs, for general and special lighting applications where by combining individual light spectra consisting of the phosphor mixtures used resulting in white light of one or more particular correlated color temperatures or colored light composed of different wavelengths.
• the generated light spectra can furthermore have certain properties, such as: B. in the case of white light spectra different levels of activation of Melatoninsynthese in
• phosphor mixtures which comprise i.) One or more compounds (i) of the formula (1) or formula (2)
• M 1 one or more alkali metal elements
• M 2 Zr and / or Hf
• A Na and / or K
• M 1 B, Al, Ga, In, Tl and / or Sc;
• M 2 Si and / or Ge
• M 3 Y, Lu and / or La
• K 2 (Si, Ti) F 6 Mn 4+ ; (Ba, Sr, Ca) 3 MgSi 2 O 8 : Eu 2+ , Mn 2+ ; Ba 2 (Lu, Y, Gd) i-xTb x (B0 3 ) 2 Cl: Eu 2 + / 3 + (where 0 ⁇ x ⁇ 1); Ba 2 Mg (B0 3 ) 2 : Eu 2+ ; La 2 O 2 S: Eu 3+ ;
• w (iii) 0 to ⁇ 45% by weight; wherein w (i) denotes the mass fraction (wt .-%) of the compound (i), w (ii) denotes the mass fraction (wt .-%) of the compound (ii) and w (iii) the mass fraction (wt .-% ) of the compound (iii), in each case based on the total mass of the phosphor mixture; with the proviso that comprising phosphor mixtures
• the phosphor mixtures according to the invention can be used in one
• light-emitting device for converting blue, violet and / or ultraviolet radiation into light having a longer wavelength.
• the present invention provides a light-emitting device having at least one primary light source and at least one phosphor mixture according to the invention.
• an illumination system contains at least two light-emitting devices, preferably LEDs, wherein the at least two light-emitting devices emit light with the same color location and / or color rendering index and / or the same correlated color temperature and wherein the light of the at least two light-emitting devices differs from the spectral composition, characterized in that each of the at least two light-emitting devices at least two different Phosphors, at least one of the phosphors being excitable by violet light and optionally by ultraviolet light and at 450 nm having a relative excitability of ⁇ 65%, preferably ⁇ 60%, more preferably ⁇ 55%, more preferably ⁇ 40%, and most preferably ⁇ 30%, and wherein the maximum excitability in the excitation spectrum corresponds to 100%.
• a dynamic lighting system which contains two of the light emitting devices according to the invention, wherein the light emitting devices emitting light with the same color location and / or the same color rendering index and / or the same correlated color temperature, characterized in that the light of the light emitting devices with respect to the spectral composition different from each other.
• At least one of the phosphors present in the phosphor mixtures At least one of the phosphors present in the phosphor mixtures,
• this phosphor is in the violet spectral range (400 to 430 nm) and optionally in the ultraviolet spectral range (100 to 399 nm) and / or partially in the blue spectral range (431 to about 449 nm) can be excited to emit light, but does not appreciably absorb light in the spectral region of> 450 nm, which means that at 450 nm the relative excitability is ⁇ 65%, preferably ⁇ 60%, more preferably ⁇ 55%, more preferably ⁇ 40% and most preferably ⁇ 30%, wherein the maximum excitability in the excitation spectrum corresponds to 100%.
• This spectral range (> 450 nm) includes partially blue, cyan, green, yellow, orange and red light. For this reason, the mass fraction of at least one component of the phosphor mixture can be varied independently of the mass fractions of the other constituents, without it being due to the mutual influence of the respective absorption and
• Figures 2 and 3 show excitation spectra of the compounds (i) which are used as non-reabsorbing phosphors in the phosphor mixtures according to the invention.
• the relative excitability of a phosphor can be determined from the excitation spectrum as follows: The maximum value of the excitation spectrum is set to 100% as a reference value, all other values, which are generally lower than or equal to the maximum value, are then calculated as a percentage of the maximum value and according to the wavelength of the
• ultraviolet light is defined as light whose emission maximum is between 100 and 399 nm, as violet light denotes light whose emission maximum is between 400 and 430 nm, blue light denotes such light, whose emission maximum is between 431 and 480 nm, as cyan light, whose emission maximum lies between 481 and 510 nm, as green light, that of
• Fluorescent mixtures are used, can be well excited in the violet spectral range for light emission. Due to the laws of additive color mixing, three primary colors are always unique
• a partial aspect of this is, for example, the activation (the wakefulness) by light. This is closely related to the content of the hormone melatonin in the human body. Melatonin acts as a synchronization transmitter for the inner clock of the human being to adapt this inner clock to the light-dark rhythm of the daylight. The information about the light gets over certain
• the melatonin suppression has a spectral response curve, with the help of which in principle the level of melatonin suppression of a given light spectrum can be calculated.
• the spectral efficiency curve and the corresponding formulas are described in detail in DIN SPEC 5031-100 of August 2015.
• Melatoninunterd Wegung a wavelength maximum in the range of about 480 nm, more precisely to Brainard 464 nm and to Thapan 468 nm, ie in the blue region of the spectrum, and a significant decrease between about 520 nm and 560 nm. Radiation with wavelengths greater than about 560th nm therefore has very little potential to suppress melatonin release.
• Composition can be effected, for example, by varying the mass fraction of at least one component (phosphor) of the phosphor mixture.
• Corresponding LED spectra are shown in FIGS. 4 to 6.
• Lighting systems can, for example, change the spectral profile of the light emitted from the luminaires, depending on the time of day, in order, for example, to adapt the correlated color temperature to natural daylight.
• Color temperature also to vary the level of melatonin suppression of the emitted spectra without other characteristic parameters associated with the spectral profile, such as the general
• Color rendering index also forced to vary. This is achieved by a complex structure via the addition of 4 basic spectra
• the basic spectra can consist of monochromatic pure semiconductor LEDs as well as of phosphor-converted LEDs.
• a clear advantage of the illumination system according to the invention compared to similar concepts is based on the fact that, for example, with only two light channels, each consisting of a white light spectrum and both having a nearly identical color location, with simple additive combination realizes a continuous shift in the level of melatonin suppression can change without changing the color location. This significantly reduces the complexity of a dynamic realized thereby
• Lighting system In addition to this advantage is in addition to call the reliability, because even if one of the light emission channels fails, the emitted light of the remaining channel still has a common white point and can be used for general lighting. In a complex multi-channel system, which uses, inter alia, monochromatic emitting LEDs, this advantage is no longer given.
• FIG. 1 Diagram for suppression of melatonin release in FIG.
• FIG. 4 Light emission spectra of LED examples 1 and 2.
• FIG. 5 light emission spectra of LED examples 3 and 4.
• FIG. 6 Light emission spectra of LED examples 5 and 6. Definitions
• phosphor or “conversion phosphor”, which are used herein as synonyms, refer to a particulate fluorescent inorganic material having one or more emissive centers.
• the emitting centers are formed by activators, usually atoms or ions of one
• Rare earth element such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and / or atoms or ions of a transition metal element such as Cr , Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and / or atoms or ions of a main group metal element, such as Na, Tl,
• Examples of phosphors or conversion phosphors include garnet-based phosphors, silicate-based phosphors,
• Phosphor materials in the sense of the present invention have no ouanten- limiting effects.
• Such non-quantum limited phosphor materials may be phosphor particles with or without a silicon dioxide coating.
• emission wavelength shift is understood to mean that one conversion phosphor is compared to another or similar
• Conversion luminescent light emits light at a different wavelength, that is shifted to a smaller or larger wavelength.
• the phosphor mixture according to the invention can be present as bulk material, powder material, thick or thin layer material or self-supporting material in the form of a film. Furthermore, it may be embedded in a potting material.
• the individual phosphors in the phosphor mixture may include adjunct materials, such as one or more coating materials.
• potting material refers to a translucent
• the translucent matrix material may be a silicone, a polymer (formed from a liquid or semi-solid precursor material such as a monomer)
• Epoxy a glass or a hybrid of a silicone and epoxy.
• Specific but non-limiting examples of the polymers include fluorinated ones
• Polymers polyacrylamide polymers, polyacrylic acid polymers, polyacrylonitrile polymers, polyaniline polymers, polybenzophenone polymers, poly (methyl methacrylate) polymers, silicone polymers, aluminum polymers, polybisphenol
• Silicones can gels such as Dow Corning ® OE-6450, elastomers such as Dow Corning ® OE-6520, Dow Corning ® OE-6550, Dow Corning ® OE
• the potting material may be a (poly) silazane, such as
• MOPS modified organic polysilazane
• PHPS Perhydropolysilazane
• a (poly) siloxazane It is preferred that the proportion of the phosphor mixture, based on the potting material, in the range of 3 to 80 wt .-% is.
• coating material refers to a material that has a
• Coating forms on the surface of a phosphor particle Coating forms on the surface of a phosphor particle.
• Coating is used herein to describe one or more layers of material provided on another material that partially or wholly covers the outer surface or solvent accessible surface of the other material at least partially in the internal structure of the
• Phosphor which has been coated penetrate, provided that the coating as a barrier nor sufficient protection against external physical influences or the passage of potentially harmful substances, such.
• Coating material provides the phosphor with additional functionality, such as reduced sensitivity to heat, reduced
• Surface of the particles of the phosphor can be smoothed by the application of one or more coating materials. Such surface smoothing enables good processability of phosphor and reduces unwanted optical scattering effects of the emitted light on the surface of the material, resulting in increased efficiency.
• Suitable materials for the coating are, in particular, metal oxides and nitrides, in particular earth metal oxides, such as Al 2 O 3, and earth metal nitrides, such as AlN, and also SiO 2.
• the coating can be carried out, for example, by fluidized bed processes or wet-chemical. Suitable coating methods are known, for example, from JP 04-304290, WO 91/10715, WO 99/27033, US 2007/0298250, WO 2009/065480 and WO 2010/075908.
• the aim of the coating can be a higher stability of the phosphors, for example against air or moisture.
• the aim can also be an improved coupling and decoupling of light by a suitable choice of the surface of the coating and the refractive indices of the coating material.
• the present invention relates to a phosphor mixture
• a phosphor mixture comprising one or more compounds (i) of formula (1) or formula (2), one or more compounds (ii) selected from the group of blue and cyan emitting phosphors, and / or a or a plurality of compounds (iii) selected from the group of orange or red emitting phosphors as defined in claim 1.
• the phosphor mixture according to the invention thus comprises one or more compounds (i) and at least one or more further compounds which are selected from the compounds (ii) and (iii).
• phosphor mixtures which comprise one or more compounds (i) and one or more compounds (ii); Phosphor blends comprising one or more compounds (i) and one or more compounds (iii); and phosphor mixtures comprising one or more compounds (i) and one or more compounds (ii) and one or more compounds (iii).
• the compounds of formula (1) are pyrosilicate phosphors, which are known from WO 2016/173692 AI.
• the compounds of formula (2) are pyrosilicate phosphors, which are known from WO 2016/173692 AI.
• Alkaline earth aluminate phosphors which are known from WO 2016/150547 AI.
• the disclosure of WO 2016/173692 A1 and the disclosure of WO 2016/150547 A1 are hereby incorporated by reference into the present patent application.
• the compounds (i) of the formula (1) or formula (2), as well as the corresponding preferred embodiments, are charge-neutral, ie, that the positive charges of the cationic elements of the grid and balance the negative charges of the anionic elements of the lattice.
• the compound (i) of the formula (1) in the phosphor mixture according to the invention is represented by the formula (3):
• M 1 Li, Na, K and / or Rb
• M 2 Zr and / or Hf
• the compound (i) of the formula (1) or (3) contains not more than one of Ba, Sr and Ca, preferably Ba or Sr.
• the ratio of the alkali metal elements within the given Molecular formula be adapted freely.
• the ratio of Li, Na, K and Rb can be freely adjusted within the predetermined parameters. It is preferred that M 1 in formula (1) and (3) is Na and / or K.
• the ratio of Zr and Hf can be freely adjusted within the given empirical formula. It is preferable that M 2 in formula (1) and (3) is Zr.
• the preferences are as above
• the compound (i) has the formula (1) or the formula (3)
• Europium is incorporated as a dopant in the form of divalent Eu 2+ on the lattice site of Ba and replaces it.
• the compounds of formula (1) or (3) can be excited by ultraviolet and / or violet light, preferably from about 370 to about 430 nm, and have emission maxima in the green spectral range of
• Particularly preferred compounds (i) of the formula (3) are compounds of the formulas (3a) and (3b):
• M 1 Na and / or K
• M 2 Zr and / or Hf
• formula (3a) and / or (3b) 0 ⁇ a ⁇ 0.6.
• a 0.
• Table 1 Particularly preferred compounds of the formula (3).
• the compound (i) of the formula (2) in the phosphor mixture of the invention is represented by the formula (4): (Ba 1 2) 2-Ca 1-dv-yEudAyM 1 -eM 2 M 2 O-e-yNe + vXx + y (formula (4)) with:
• A Na and / or K
• M 1 B, Al, Ga, In, Tl and / or Sc;
• M 2 Si and / or Ge
• M 3 Y, Lu and / or La
• 0 ⁇ d ⁇ 1.0 more preferably 0.03 ⁇ d ⁇ 0.25, most preferably 0.05 ⁇ d ⁇ 0.20;
• 0 ⁇ y ⁇ 0.1-a more preferably 0 ⁇ y ⁇ 0.05-a, most preferably 0 ⁇ y ⁇ 0.03-a;
• the compound (i) of the formula (2) or (4) contains more than one of Ba, Sr and Ca, the ratio of Ba, Sr and Ca can be freely adjusted within the given empirical formula. In a preferred embodiment, the compound (i) of the formula (2) or (4) contains ⁇ 10 atom%
• the compound (i) of the formula (2) or (4) contains not more than one of Ba, Sr and Ca, more preferably Ba or Sr.
• the ratio of Na and K can be within the given
• compound (i) of formula (2) or (4) contains ⁇ 10 at% of elements B, Ga, In, Tl and / or Sc, more preferably ⁇ 5 at% of elements B, Ga , In, Tl and / or Sc, and most preferably ⁇ 3 atomic% of the elements B, Ga, In, Tl and / or Sc, based on the total content of all elements M 1 . It is preferable that M 1 in formula (2) and (4) is Al, Ga and / or Sc, more preferably Al.
• the ratio of Si and Ge may be within the given
• M 2 in the formula (2) and (4) is Si.
• a trivalent element M 1 and a divalent oxide anion O 2- are replaced by a tetravalent element M 2 and a trivalent nitride anion N 3 " .
• the ratio of Y, Lu and La can be freely adjusted within the given empirical formula. It is preferred that M 3 in formula (2) and (4) La is.
• the trivalent element M 3 replaces an alkaline earth metal element Ba, Sr and / or Ca. The charge is compensated by trivalent nitride anion N 3 " .
• X in formula (2) and (4) is F. It is either possible for a monovalent alkali metal A and a monovalent anion X to replace an alkaline earth metal Ba, Sr and / or Ca and a divalent oxide anion O 2 and / or for the charge of the monovalent anion X to be replaced by a lower content of the alkaline earth metal Ba, Sr and / or Ca is compensated and / or that a part of the divalent oxide anions O 2- is replaced by two monovalent anions X.
• the abovementioned conditions for the ratio of a / b and a / c ensure that the compound is formed in the ⁇ -alumina phase and results from a ⁇ -alumina structure of composition Bao, 75AlnOi7.25, as by X-ray powder diffractometry was detected.
• the compounds of the formula (2) or (4) show a pure Bao, 75AlnOi7.25 structure of ß-Aluminum oxide, even if they contain alkali metals A or trivalent metals M 3 or halide anions X, or if they contain, for example, Sc 3+ or other trivalent cations instead of Al 3+ or with Si 4+ and N 3 " instead of
• the compounds of formula (2) or (4) can be excited by ultraviolet and / or violet light, preferably from about 370 to about 430 nm, and have emission maxima in the green spectral range of preferably about 510 to about 520 nm, depending on the exact composition.
• Table 2 Particularly preferred compounds of formula (4).
• the compound (i) of the formula (4) in the phosphor mixture according to the invention is represented by the formula (4a):
• 0 ⁇ z ⁇ 0.1, more preferably 0 ⁇ z ⁇ 0.05, even more preferably 0 ⁇ z ⁇ 0.03, and most preferably z 0;
• the compound (i) of the formula (4) in the phosphor mixture according to the invention is represented by the formula (4b):
• 0 ⁇ z ⁇ 0.1, more preferably 0 ⁇ z ⁇ 0.05, even more preferably 0 ⁇ z ⁇ 0.03, and most preferably z 0;
• the compound (i) of the formula (4) in the phosphor mixture according to the invention is represented by the formula (5):
• the phosphor mixture in addition to the one or more compounds (i) of formula (1) or (2), contains one or more compounds (ii) selected from the group of blue and cyan emitting phosphors, and one or more compounds (iii) selected from the group of orange or red emitting phosphors.
• the phosphor mixture contains only one compound each (i) and (ii) and / or (iii).
• the phosphor mixture consists of one or more compounds (i) of the formula (1) or (2) and one or more compounds (ii) selected from the group of blue and cyan emitting phosphors, and / or one or more compounds (iii) selected from the group of orange or red emitting phosphors.
• the phosphor mixture consists of a compound (i) of the formula (1) or (2) and a compound (ii) selected from the group of blue and cyan emitting phosphors, and / or a compound (iii) selected from the group of orange or red emitting phosphors.
• the compounds (ii) are selected from the group of blue or cyan emitting phosphors consisting of (Sr, Ba, Ca) 3 MgSi208: Eu 2+ ;
• the compounds (iii) are selected from the group of orange or red emitting phosphors consisting of (Sr, Ba) 3SiOs: Eu 2+ ;
• the conditions (A) and (B) of the phosphor mixture are defined as follows:
• Preferred phosphor mixtures for the generation of light spectra with different melatonin suppression levels are listed in Table 3.
• Table 3 shows preferred phosphor blend compositions that produce light spectra with different levels of melatonin suppression in the particular color temperature ranges indicated when using violet-emitting LED semiconductors as the excitation light source.
• Table 3 Preferred phosphor blends with associated color temperature and melatonin suppression ranges.
• Table 4 gives the respective individual components
• BaSi 2 0 2 N 2 Eu 2+, Lu 3 (Al, Ga) 5 0i 2: Ce 3+ and / or
• LiCaPO 4 LiCaPO 4 : Eu 2+ .
• Ba 2 Mg (B0 3 ) 2 Eu 2+ , La 2 O 2 S: Eu 3+ , (Sr, Ca, Ba) 2 Si 5 N 8 : Eu 2+ and / or (Sr, Ca, Ba) 2 Si5-x Alx N8- x O x : Eu 2+ (where 0 ⁇ x ⁇ 3.0).
• Table 4 Individual components of the phosphor mixtures shown in Table 3.
• the phosphor mixture according to the invention can be converted for use in light-emitting devices, in particular in LEDs, in any external forms, such as, for example, spherical particles, platelets and structured materials and ceramics. These forms will be
• the term "shaped body" is used to summarize the preform.
• the shaped body is preferably a "phosphor body”.
• Another object of the present invention is thus a molding containing the phosphors of the invention. The preparation and use of corresponding moldings is familiar to the person skilled in the art from numerous publications.
• Ceramics contain, in addition to the phosphor mixtures according to the invention, matrix materials, for example silazane compounds, in particular polysilazanes or polysiloxazanes.
• matrix materials for example silazane compounds, in particular polysilazanes or polysiloxazanes.
• Particularly preferred matrix materials are perhydropolysilazane (PHPS), Al 2 O 3 , Y 3 Al 5 O 2 , SiO 2 , Lu 3 Al 5 O 2 , Al 2 W 3 O 2 , Y 2 W 3 O 2 , YAlW 3 O 2, ZrW 2 0 8 , Al 2 Mo 3 Oi 2 , Y 2 Mo 3 Oi 2 , YAIMo 3 Oi 2 , ZrMo 2 O 8 , Al 2 WMo 2 Oi 2 , Y 2 WMO 2 O 12, YAIWMO 2 O 12, ZrWMoOs, Al 2MOW 2 O 12, Y 2MOW 2 O 12, YAIMOW 2 O 12 or mixtures thereof.
• Suitable matrix materials are magnesium-aluminum spinel, yttrium oxide, aluminum oxynitride, zinc sulfide, zirconium oxide, lithium iodide oxide, strontium chromate, magnesium oxide, beryllium oxide, yttria-zirconia, gallium arsenide, zinc selenide, magnesium fluoride, calcium fluoride, scandium oxide, lutetium oxide and gadolinium oxide.
• the phosphor mixtures according to the invention can also be provided as so-called “phosphor in glass” applications (PIGs), as described, for example, in WO 2013/144777 A1.
• the method according to the invention for producing a phosphor mixture as described above comprises the following steps: a) weighing a mass m (i) of the phosphor (i), a mass m (ii) of the
• step a mixing the masses of the phosphors (i), (ii) and / or (iii) weighed in step a).
• step a) the elimination of the masses m (i), m (ii) and / or m (iii) in step a) takes place successively.
• the weighing can also be done simultaneously.
• step b) is preferably carried out by means of a planetary centrifugal mixer, a roller bank, an overhead mixer, a
• the mixing process can be carried out both in the wet state (that is, the masses to be mixed are converted into a suitable mixture before being mixed
• Liquid such as. As water or ethanol, given
• water or ethanol given
• the steps a) and b) are preferably carried out at room temperature, more preferably at 20 to 25 ° C.
• Light-emitting device
• the light-emitting device contains at least one primary light source and at least one phosphor mixture, as described above.
• the primary light source is either a semiconductor light emitting diode (SLED), a semiconductor laser diode (LD) or an organic
• the primary light source of the light-emitting device may be a plasma or discharge source. Preferred are those primary light sources that emit light in the spectral range from about 385 to about 480 nm, more preferably from about 390 to about 450 nm, and most preferably from about 395 to 440 nm.
• a semiconductor light emitting diode (SLED) that forms a first group of suitable primary light sources is a two-wire semiconductor light source. It is a p-n junction diode that emits light when activated. When an appropriate voltage is applied to the leads, electrons can recombine with electron holes within the device, releasing energy in the form of photons. This effect is called electroluminescence, and the color of the light (corresponding to the energy of the photon) is determined by the energy bandgap of the semiconductor.
• the structure and mode of operation of a SLED are known to the person skilled in the art.
• TCO transparent conducting oxide
• a semiconductor laser diode also known as an injection laser diode or ILD, is an electrically pumped semiconductor laser in which the active laser medium is formed by a pn junction of a semiconductor diode similar to that in an S-LED. Construction and operation of an LD are known in the art.
• the LD is the most widely used type of laser for many applications, such as for example, fiber optic communication, barcode readers, laser pointers, CD and DVD and BLURAY-DISC readers and recorders, or similar, laser printers,
• a third group of suitable primary light sources comprises so-called organic light-emitting diodes (OLEDs), in which the emitting
• the electroluminescent layer is an organic compound film that emits light in response to an electric current.
• This layer of organic semiconductor is located between two electrodes. Typically, at least one of these electrodes is transparent. Structure and functionality of
• OLEDs are known to the person skilled in the art.
• the light emitting device is a light emitting diode (LED). lighting system
• the lighting system according to the invention contains at least two
• each the at least two light-emitting devices contain at least two different phosphors, wherein at least one of the phosphors is excitable by violet light and optionally by ultraviolet light and at 450 nm a relative excitability of ⁇ 65%, preferably ⁇ 60%, more preferably ⁇ 55%, stronger preferably ⁇ 40%, and most preferably ⁇ 30%, and wherein the maximum excitability in the excitation spectrum corresponds to 100%.
• the light of the at least two light-emitting devices differs in terms of spectral composition when at least one parameter associated with the spectral emission profile, e.g. the color locus, the color rendering, the correlated color temperature or the
• the first light-emitting device different from the corresponding parameter of the second light emitting device.
• the amount of the difference in the x color coordinates of the color locations to be compared of the different light emitting devices in the CIE-1931 standard (2 ° standard observer) standard is> 0.007; this also applies to the amount of the difference of the y color coordinates (valid in the same color system) of the color locations to be compared;
• the at least two light emitting devices in the lighting system are light emitting devices according to the invention as described above.
• the lighting system of the present invention is a dynamic lighting system.
• the present invention relates to a dynamic lighting system comprising at least two light emitting devices according to the invention, wherein the at least two light emitting devices according to the invention emit light with the same color location and / or same color rendering index and / or the same correlated color temperature, characterized in that the light of at least two light emitting according to the invention
• Devices differ in terms of spectral composition from each other.
• Devices in the dynamic illumination system differ in terms of spectral composition when at least one parameter associated with the spectral emission profile, e.g. the color locus, the color rendering, the correlated color temperature or the
• the first light-emitting device according to the invention differs from the corresponding parameter of the second light-emitting device according to the invention, as further defined above.
• the phosphor mixtures according to the invention can be used in one
• light-emitting device for converting blue, violet and / or ultraviolet radiation into light having a longer wavelength.
• the light-emitting device is preferably a light-emitting diode (LED) for use in general lighting and / or in special lighting.
• LED light-emitting diode
• the phosphor mixtures according to the invention are used in small amounts, they already give good LED qualities.
• the LED quality is described with conventional parameters, such as the color rendering index, the correlated color temperature, the lumen equivalent or absolute lumen or the color location in CIE x and y coordinates.
• the Color Rendering Index is a unitary photometric quantity known to those skilled in the art that compares the color fidelity of an artificial light source to the color fidelity of given reference light sources (the reference light sources have a CRI of 100 and the exact definition of the CRI can be found in FIG CIE Publication 13.3-1995).
• Correlated Color Temperature is a photometric quantity known to those skilled in the art with the unit of Kelvin. The higher the Numerical value, the higher the blue component of the light and the colder the white light of an artificial radiation source appears to the viewer.
• the CCT follows the concept of the black light emitter, whose color temperature describes the so-called Planckian curve in the CIE diagram.
• the lumen equivalent is a photometric quantity known to those skilled in the art with the unit Im / W, which describes how large the photometric luminous flux in lumens of a light source is at a certain radiometric radiation power with the unit Watt. The higher the lumen equivalent, the more efficient a light source is.
• the lumen is a photometrical photometric quantity which is familiar to the person skilled in the art and describes the luminous flux of a light source, which is a measure of the total visible radiation emitted by a radiation source. The larger the luminous flux, the brighter the light source appears to the observer.
• CIE x and CIE y represent the coordinates in the familiar CIE standard color diagram (in this case normal observer 1931), which describes the color of a light source.
• Ingredients in the compositions always add up to a total of 100%. Percentages are always to be seen in the given context.
• Phosphor component 1 is used together with mi_s2 (in g) of the phosphor component 2 listed in the respective LED example, mi_s3 (in g) of the phosphor component 3 listed in the respective LED example, and mi_s4 (in g) of the phosphor component listed in the respective LED example 4 weighed and homogeneously mixed in a planetary centrifugal mixer.
• the mixture is mixed with an optically transparent binder (eg silicone) and mixed so that the phosphor concentration in the optically transparent binder is expressed by CLS (in% by weight).
• an optically transparent binder eg silicone
• CLS in% by weight
• the violet-emitting semiconductor LEDs used in the present examples for LED characterization have emission wavelengths in the range of 405 nm-415 nm and are operated at 350 mA current.
• the photometric characterization of the LED is done with a spectrometer of the
• the LED is characterized by the determination of the wavelength-dependent spectral power density.
• the spectrum thus obtained of the light emitted by the LED is used to calculate the color point coordinates CIE x and y, the correlated color temperature (CCT). and, if necessary, the brightness or the melanopic yield of the visible radiation K m ei, v used in accordance with DIN SPEC 5031-100.
• Table 5 shows LED examples 1 and 2 of a cold-white emitting LED with non-reabsorbing blue and green phosphors or a reabsorbing green phosphor.
• Table 5 LED examples 1 and 2 with phosphor mixtures containing non-reabsorbing or reabsorbing phosphor mixture components.
• LED Examples 1 and 2 show a non-reabsorbing system as compared to a reabsorbing system where the improvement in overall efficiency can be shown.
• FIG. 4 shows the light emission spectra of LED examples 1 and 2.
• Table 6 shows LED examples 3 and 4 of a neutral-white-emitting LED with a low melatonin suppression level and a high melatonin suppression level, respectively.
• Table 6 LED examples 3 and 4 with phosphor mixtures with high or low melatonin suppression level.
• the LED examples 3 and 4 show two LED spectra which have a different level of melatonin suppression at almost identical color location and which can therefore be combined with one another in a 2-channel illumination system in the manner shown here.
• FIG. 5 shows the light emission spectra of LED examples 3 and 4.
• Table 7 shows LED examples 5 and 6 of a neutral white emitting LED having a low melatonin suppression level and a high melatonin suppression level, respectively.
• Melatonin suppression level Melatonin suppression level green emitting phosphor green emitting phosphor according to compound (i) of compound (i) of the
• Table 7 LED examples 5 and 6 with phosphor mixtures with high or low melatonin suppression level.
• the LED examples 5 and 6 show two LED spectra which have a different level of melatonin suppression at almost identical color location and which can therefore be combined with one another in a 2-channel illumination system in the manner shown here.
• FIG. 6 shows the light emission spectra of LED examples 5 and 6.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Physics & Mathematics (AREA)
• Computer Hardware Design (AREA)
• General Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Manufacturing & Machinery (AREA)
• Optics & Photonics (AREA)
• Electromagnetism (AREA)
• Luminescent Compositions (AREA)
• Led Device Packages (AREA)
• Liquid Crystal Substances (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=58266906

Family Applications (1)

Country Status (8)

Families Citing this family (5)

Family Cites Families (22)

• 2018
  • 2018-03-05 EP EP18709529.4A patent/EP3592826A2/de not_active Withdrawn
  • 2018-03-05 US US16/492,014 patent/US10907095B2/en active Active
  • 2018-03-05 CN CN201880016605.6A patent/CN110382664A/zh active Pending
  • 2018-03-05 SG SG11201908185R patent/SG11201908185RA/en unknown
  • 2018-03-05 KR KR1020197029107A patent/KR20190126363A/ko unknown
  • 2018-03-05 JP JP2019548679A patent/JP2020511569A/ja active Pending
  • 2018-03-05 WO PCT/EP2018/055277 patent/WO2018162375A2/de unknown
  • 2018-03-07 TW TW107107520A patent/TW201840824A/zh unknown

Also Published As

Similar Documents

Legal Events