DE2018352C - Up-transforming fluorescent substance for converting infrared radiation into visible radiation and its use - Google Patents

Description

6. Light converter according to claim 5, characterized in that they work steadily at frequencies which are above characterized in that the phosphor layer (8) are distributed over the visible and infrared spectrum, the light-emitting diode is firmly attached. 40 Since the adaptability in terms of the

7. Light converter with a fluorescent light available constant output frequency at Fabric according to claim 1, characterized in that gas lasing is the greatest concentrated that the fluorescent phosphor as a single crystal technical development on this type of laser, while is present, which as a stimulable medium of the development of solid-state lasers in the veroptischen Coherent light transmitters remained limited for 45 years. There is therefore only an optical resonator is arranged and a few basic types of solid-state lasers. As steady is excited with a radiation, the solid-state lasers operating at longer wavelengths are of the category than is the coherent emitted radiation. with optical excitation radiation only facilities known with trivalent neodymium, the

so work within the red spectral range.

The invention is based on a quantum counter material for converting infrared radiation into visible radiation, which consists essentially of alkaline earth halide, the ytterbium in addition

The invention relates to an up-transforming 55 containing holmium or erbium. According to the invention

the fluorescent phosphor for conversion infra is approximately the alkaline earth halide material

red radiation into visible radiation, which im according to the formula

consists essentially of alkaline earth metal halide, the _ö , »» «c vu \ ν

Contains ytterbium in addition to holmium or erbium. Ba (M ₁ REyYb ₁ - * - ,,) ,, X _{t + 3e} As is well known, there are two different compounds 60, where M is at least one element Types of devices for generating coherent - from the group consisting of Y, Lu, Gd, Ce, Sc, La,

ter or incoherent electromagnetic radiation Ga, In and Al, RE is at least one element from the

in the range of visible wavelengths. The one set up group consisting of Er and Ho is shown, X to-

ment indicates electroluminescent (incoherent), sees- at least one halogen and where χ is a range

light sources emitting cash, while 65 from 0 to 0.95, y a range from 0.01 to 0.3 and λ

the other facility uses lasers. can run through a range from 0.05 to 4.

Visible light emitting electroluminescent In an embodiment of the invention it is proposed that Institutions can offer numerous forms of training that include the element Er for RE and the element F for X.

3 4

are used and that each value range of details is explained, specifically with reference

0 to 0.82, y such a vpn 0.03 to 0.2 and «on the drawings. Herein shows

from 0.4 to 3. F i g. 1 an Ausfühningsbeispiel in which a

In one embodiment of the invention, a diode emitting in the infrared spectral range is provided If M corresponds to the element Y and «comprises a layer S with a fluorescent layer according to the invention from 0.6 to 1.5. can be seen in front view,

Preferably, α is equal to 1 ± 10%. F i g. 2 an energy level scheme for the loose Yb ³⁺ ,

For a light converter with a fluorescent Er * +, Ho ⁸⁺ with a white phosphor according to the invention indicated on the ordinate, numbers are proposed, with the illustrated energy states that this fluorescent phosphor was observed from the layer that was observed inside the host crystal, radiation-emitting surface of a GaAs -L Leucht- Fig. 3 one with infrared excitation radiation

diode covered operated diode laser, which is equipped with an inven-

In a preferred light converter, the connection according to the invention adheres to the side phosphor layer on the light-emitting diode. opinion

For a further light converter, it is proposed 15. A GaOium arsenide illustrated in Figure 1 The fluorescent phosphor is present as a single crystal, diode 1 contains a p-n interface 2, between a as a stimulable medium of an optical transmitter p- and an n-area 3 or 4. The diode is through for coherent light within an optical one, a disk-shaped anode and an annular one Resonator is arranged and with a radiation cathode 6, which excites an energy not shown that is connected with a longer wave than the coherent ao supply, in the forward direction emitted radiation is. stretched. Through the interface 2 is under

The invention is based on the observation that exposure to the forward bias in infrared produces any of a number of novel compounds. Part of this radiation, which contains Yb ³⁺ , is able to be made more effective by arrows 7, runs in and through a manner of infrared radiation in wavelengths in the layer 8 of a fluorescent material after the baren spectral range to higher Frequencies invention. Under these conditions a part will convert. It is fluorescence. absorbs radiation7 within the layer; The activator ion can be the same as that which, in the above report reproduced in a larger part of this absorbed radiation, takes part in a process comprising two photons or was Er ³⁺ , although Ho ⁸⁺ as an addition or replacement participates in a higher-order photon process to be present. radiation at a visible wavelength or

For example, a combination of several visible wavelengths of higher frequency according to the invention is material doped with erbium, which is to be generated by. The exiting part of this radiation can be represented by the formula BaYbF ₆ . In addition, it is illustrated by arrows 9, as will be explained in the following description. The main advantage of the specified fluorescence, a large number of composition substances is best derived from the energy level and also from certain substitutions and the scheme according to FIG. 2. While, however, the particular additions are applicable. going description of energy levels on that

The use of this material based on carefully carried out Adsorptionsrials has proven to be favorable in connection with an electroluminescent 40 and emission studies are some Semiconductor diode proven. Such an arrangement of the information contained in the figure is merely as consists, for example, of a silicon-doped "optional conclusion to be considered in particular GaAsrDiode with a coating of the type described pave the way for the three- and four-photon pro-composition. The coating cannot take up a process, although a certain part of the obs additive or contain additives in order to adhere to the radiation emission of multiple photons improve and / or the light scattering represents a reduction process, which is a doubling adorn. In such an application example lies beyond. The scheme is enough for this purpose, the emitted light at a wavelength in the green d. H. describes the general advantages of the turned-spectral range of about 0.55 μm, and the dissolved embedding materials and in particular the The rising brightness is comparable to that of the 5 * pin-enclosed ions in terms of the quantum best BaP diodes. physics.

The new connections after the invention While the pair Yb ³ ♦ ■ - Er ³⁺ currently the most effective

can be grown as large single crystals with a high degree of upward conversion effected, with regularity. Therefore, the pair Yb ³⁺ - Ho ^{3 f can} also generate a substantial amount of such a crystal, also as a fluorescent medium 55. The last-mentioned pair in an optical transmitter for coherent light causes emission to only be used in the green range. This stimulable medium has a wavelength of about 5400 A. Unlike the favorable optical excitation radiation pair Yb ³⁺ - Er ⁸⁺ , which under certain circumstances is operated from a narrowly limited light source, for example in a red wavelength range from a GaAs Diode, and is able to emit at 60, does not have a photon addition protein of a higher order characteristic of the fluorescent substance, which has a perceptible wavelength. Such a wavelength is as shown by the output variable. This fact, which was possibly mentioned, is in the green area. Since this stimulability is close to using both activator ions together in the bare medium, three energy levels (of type II) in a compound in order to intensify the emission in room temperature or four energy levels in the low-pressure region or otherwise have a low temperature, continuous operation, the visible colored output variable is possible for another. to adjust the desired value.

The invention is explained in more detail below. The ordinate units are in wavelengths per Centimeters (cm ~ i) indicated. According to new compositions, these units can be essential]

at wavelengths in Angstrom units (A) or was observed directly. A detailed one

Micrometer (μπι) according to the following relationship umge- explanation with regard to the dependency of this

will be changed: Lifespan of these compositions was ι

X0> .10 * S now developed. It is believed that the same i

Wavelength = 7777, ZT ^{A =} ~ ^ ΓΪΓ - ΖΓ ^μτη ' Structure or the same dependence on the

Wave number wave number composition, soft this long life j The left part of the diagram concerns the corresponding effects, for the effective upward ones

the energy states of Yb ³⁺ in a material conversion of the partial third photon

according to the invention. An absorption in Yb * + results in 10 processes responsible for erbium rot and also, j

an energy increase from the ground state ¹ F ₇ /, through the second photon process, to holmium green. j

* F ₆ /, - state. This absorption defines a band, The Effective Upward Conversion '

which is in the range of 9800 to 10 800 cnr '. is, as is understood, not exclusively such a ]

The rest of FIG. 2 is added in connection with the condition of substantial intermediate life!

postulated excitation mechanism explained. Write all 15. Other essential factors, including- <

Energy level values and all Hch lifetimes of excited states of higher states indicated in the figure Decay processes have been confirmed experimentally. Order, for example ⁴ S ", and ⁴ F ₁ /, in erbium As a result of the absorption of the GaAs diode as well as' S, in holmium and also the related

Radiation emitted by Yb ¹⁺ becomes a quantum for borrowed probabilities of the different types

the emitting ion Er ** received (or, as in $ 0, from nonradiative transitions, which with the

binding. is discussed with the figure, for Ho * ⁴ ). The - radiation transitions compete are considered

the first transition is denoted by 11. To draw the suggestion.

The erbium emission B is partly due to over-energy ( denoted by m ) almost exactly the decay of a third quantum from Yb ¹⁺ to Er ·· transition from Yb ^{8 +} adapted. A similar transition, called »5, whereby the ion of Er ⁴ S, /, to Er ¹ Cl ,, which leads to an excitation of Ho ** to the ¹ I ₄ -Zu with the simultaneous generation of a phonon (supernatant, requires a simultaneous delivery of even i, 13) is encouraged. This is followed by an internal one or more phonons (+ P) - the Er-zu- decay process on Er ⁴ G ,, / ,, which in turn stood ⁴ I “/ i has a substantial lifetime; A decay process on Er ⁴ F ₉ /, through the transition of a second quantum from Yb ⁸⁺ promotes the 30 of a quant y back to Yb '* with a simultaneous ore transition! 2 to the Er ⁴ F _{; i} condition. a phonon (übeigang 13 ') is possible. There <

A transition of a second quant to the Ho ⁸ * ⁴ F ₉ / »level is achieved by at least two ver

gives a stimulus to Ho * S ,. An inner separated mechanisms occupied. An experimental

sounding process is determined by a confirmation in this figure actually from the determined,

wavy arrow (|) reproduced. In the erbium the fact shows that the emission of B comes from the who

the second photon level ( ⁴ F ₇ /,) a lifetime of the injected intensity is dependent on which

which, due to the presence of closely following between the characteristic intensity of a Dre

lower levels is very short, which is a photon process and that of a two-photon

rapid decay to the ⁴ S, /, - state under process for the BaY F _s material. The emission /?

Generation of phonons leads. 40 in the red spectral range is around 15 250 cm The first major emission of Er ¹ * occurs or 0.66 μπι.

from the ⁴ S, /, - state (18 200 cm- ¹ or 0.55 μπι in the while the emission in the green and red spec-

green spectral range). This emission is predominant in the central area, numerous others lie

Figure by a broad (double-lined) arrow A. emitted wavelengths from which the next

specified. The reversal of the second photon 45 stronger, labeled mi · C, in the blue spectral range

excitation, the radiationless transition of a quantum (24 400 cm ¹ or 0.41 μπι) is. This third emission

from ⁴ F ₇₁₁ back to Yb ¹ * must go with the fast one from the Er ¹ H ₉ Z ₁ -NiVCaU, that in turn

Phonon relaxation on Er ⁴ S ₉ /, compete and is occupied by two mechanisms. The first

is not a limitation. The phonon ^{relaxation mechanism is energy absorbed by a phonon on Er 4} F ,,, also competes with the emission A 50 process of Er ⁴ G _n ,,. The other

and contributes to the emission of ⁴ F ₉ ; The measure, mechanism is a four-photon process, accordingly

up to which this further decay process develops in the fourth quantum from Yb ¹⁺ to Er ¹⁺ under excitation

is borrowed depends on the composition. That of the ion from the ^, ", - level (transition 14) over-

Overall considerations regarding the relationship between. This step is followed by an internal decay process see the predominant emission tone processes and ss on Er ¹ D ₄ / ,, from where energy back to Yb-

the composition will subsequently be transferred under the, with a decay process

»Composition« section explained in more detail. from Er ¹⁺ to ⁴ H _rt (transition I4 "> is brought about. The emission A in the green spectral range at A significant emission of holmium occurs

Wavelengths of about 0.55 μm corresponds to that only due to a two-photon process. the which is known to have been observed for him in LaF. 60 emission prevails from the Ho * S * state in the green

According to the invention it is postulated that the observed spectral range (18 350 cm " ¹ or 0.54 μητ). The

high conversion efficiency results in part from the mechanisms responsible for this

the observed life span of the Er * I _{1I / t} -An- from F i g. 2 as well as the preceding explanation,

excitation level results. A substantial service life The device according to FIG. 3 is a by optistcigert See the probability of a second photo from excited solid-state lasers

nenübergangec to the * F ", - level, from where 20 with a single stimulable crystal rod 21,

possibly a !! mission (A) in the green spectral range which consists of a crystal according to the invention

goes out. That this lifetime exists in the case of the compositions according to the invention. The Stab21 is with

2 Gl8 £ 352

7; 8th

reflective layers 22, 23 are provided to form a to, y = 0.3, the preferred range between optical Fabry-Perot resonator. When y = 0.03 and >> = 0.2. The broad and before the laser 20 is supposed to work as an optical transmitter, added minima can be based on the output variable that is distinguishable for the unarmed one of the two layers, for example the layer eye, or the 22, be fully reflective, while the other layer is light Observability under normal room beds, for example layer 23, partially transparent lighting conditions. The upper limits are based on forms. As with a customary, optically stimulated on the observation that much higher values solid-state laser, the layers 22, 23 from a. (above j> = 0.3) cause a drop (and that series of dielectric layers be composed. Appropriate amounts widened to a considerable

The rod 21 draws its excitation energy from io reveal improvement lead (y = 0.2). ■

a radiation source 24 which, in the case of the illustrated embodiment, the total content of trivalent ions (in contrast to the exemplary embodiment, consists of one or more infrared one Ba * 'ion) within a few diodes 25 which emit radiation on top of one another. Each of these following narrower alpha ranges can be defined. The diode can be similar to the one which extends in the broadest range from 0.1 OS to 4. These heal in FIG. 1 is shown. Each diode is _i5 wide range based on the fact that an overrun provided accordingly with LlektrodenanschJüssen 26,27, any limit in the material level causes a current decrease of the brightness (not shown) to their excitation to a. The minimum value source are connected in the forward direction. With is simply based on the need for an optimal arrangement, for example the presence of sensitizer and activator ions, the individual diodes can form a hollow cylindrical ao to generate an emission. A preferred tube can be combined, which concentric area lies between = 0.4 and = 3, which surrounds the rod 21. The basis for these limits is generally approximate

The compositions according to the invention can be the same as for those given above

nen limits represented by the following general formula. It should be noted that a small observable

become: »5 Brightness range between the two areas

n./w «π VK λ γ occurs, i.e. between the broad and preferred

Minima and / or between the broad and preferred Here, M represents at least one of the three-valued th maxima.

ions of yttrium, lutetium, gadolinium, Ccr, the closest range of alpha values which is for

Scandium, lanthanum, gallium, indium or Alu · 30 represent the purposes according to the invention even more strongly; Kh is at least one of the trivalent vomigen's. extends from α = 0.6 to <x = 1.3. Ions of erbium and holmium; X is at least The brightest samples currently being produced all fall within one of the monovalent halogen ions (fluorine, chlorine, this range.

Bromine, iodine). According to the common chemical noun · It has been observed that different members

The information in the index Numbers of Ions 35 of the general formula represents a different critical or represent atoms; if an index is not available, the structure must have a stallographic structure. Line crystallography these Number equals 1. If other expressions see form of assumed hexagonal structure no representation with regard to the exact shape as the only phase with a nominal value of α - 1 any of the included compositions. While compositions outside of this is specified (some of these can be composed of 40 nominal values of «- 1 but still within tongues, while the other solid solutions generally fall within the preferred range of 0.0 to 1.5 Connections can be), which are in general two-phase, if you look at the extreme values Formula information used regularly, sewing on, remains a certain part of the preferred to define a connection. . structural form assumed to be in hexagonal form.

The M-ion is a diluent and carries 45. Improved results were tentatively assigned to the not necessary either directly to an absorption of a part of this phase,
tion or an issue. From the above it follows that the ideal

However, this is its existence, both in type and composition for the approximate alpha value, as well as in the amount, in the sense of a shift that occurs from 1. For this purpose, the preferred addition of the apparent radiation 50 ssmmpmeiMine is effective in the range of λ - 1 ± 10 ° /. In other circumstances the lying therefrom can be defined.

If the alpha value is significantly smaller than i, the following reduction in Yb or RE will result in a reduction in concentration. The number was observed that trivalent ions, for example of M ions or the value of χ can change from any ions provided with the index α from 0 to 0.95. The lower limit does not require any explanation, while the upper limit may be minimal. Insofar as such an intermediate space corresponds to the Yb and RE content, which is carried out by fluorine for discharge, the protruding visible radiation emission remains necessary if the given general formula is essentially correct this is easy for the unarmed human eye to take into account that an ÄnzaSil should be distinguishable from fluorine ion. A preferred range Se equal to the value α can be present in spaces extends from χ - 0 to χ - 0.82. The preferred, as far as such a discharge does not occur, the maximum value is based on the observation that some of the ions labeled with the index α have two compositions at one level to illuminate. In this form, the Y and RL ionic capacities do not contribute to the desired transformation under normal room lighting and which can easily be observed under normal room lighting conditions. 65 are regarded as impurities.

The limits for RL (Aktrvalorion Er "or Die I ntladen) can also be determined by the use

Ho * ⁴ ) are given by the requirement for the brightness of other space ions, for example ti ¹ 'am. The broad range runs from y - 0.01, even thin anion errors occur.

209 eat? 37

9 10

Other requirements are generally those darüber'.aufgeheizt is for temperatures of 100 ⁰ C or fluorescent phosphors together. Various requirements require the exclusion of moisture and acidic impurities, which cause undesirable absorption. The work described in the masts has the effect of causing or otherwise "poisoning" the hydrogen fluoride according to the invention or, in an inert atmosphere, systems are to be avoided. When S carried out by nitrogen or Hehunt, general provision, compositions commensurate with Upon completion of the process step of a degree of purity in which one zonal conditioning the Banum- _V on appears? InfmReinhdtsgradvon99% of the starting materials fluoride as a water-white crystalline mass containing a emanates. A further improvement results, however, may or may not be single crystal, by increasing the purity to at least io. In the BaF ₁ · RFa system, the RF is added in the form of ^{99,999 ° / of} ytterbium trifluoride (.YbF ₃ ). The Ver-

Useful fluorescent phosphors can be produced by bonding the oxide Yb ₁ O, with ceramic processes in which hydrogen fluoride reacts at elevated temperatures the initial additives which are left together to form:

lead, be intimately mixed and burned. 15 Yb ₁ O, + 6HF -> 2YbF, + 3H ₁ O

As with the formation of other ceramic assemblies,., .-. ' u iu

Settlements can be an intermediary calcine- The reaction is in a graphite ship within runessShritt carried out at a sufficient temperature using a platinum tube. The boat with it to get a response to which a content will be based on for a sufficient period of time Pulverize «follows, for example, in a shaking» o kept at a sufficient temperature to pass through mill, as well as a final burning process. Diffusion to induce limited reaction. For the

Powders however produced can be used in an actual amount taken in the full variety of forms. If they process 24 hours. The final product appears as to be used as a coating, they can be water-clear with powder, which are finally mixed during an embedding material, examples ₅ a temperature of 1160 ⁰ C is melted. The solid mass produced in this way on a glass, for example, to adhere to it is removed from the base material as well as a reduction in the light shuttle.

To cause wastage. To this end, the YbF should be broken up, the stochiometnsch

the embedding material does not absorb any substantial amount is weighed out and it is done ion within a small number of phonons 30 an intimate intermingling with the crystalline banum of any the essential fluorescence excitation fluoride. The boat and its contents will turn have levels as well as a refractive index in an inert atmosphere of nitrogen, helium which approximates that of the phosphor. or hydrogen fluoride by a zone melt pre-invention Luminescent materials have a refraction device guided, namely first at a ratio index from about 1.7 to. Since the embedding material 35 moderately high speed of a few centimeters in no way supports the energy conversion, per hour to ensure homogeneity its content is to be kept to a minimum, that and afterwards at a relatively low feeling the purposes explained above is sufficient. speed to generate the desired kri-Es it was found that an improvement in terms of stable completion (a speed of about the brightness arises from cleaning. Since the 40 0.3 cm per hour '»I proved to be appropriate). Purification results from growth processes, which while the substances initially according to the Bridgman-

Naturally, processes can be provided for the crystallization of these substances, if it has been proven that they are to be adapted, such a procedure is generally to be recommended as a very favorable final process for this process. It turns out, for example, crystals, which by zone melting in the al? It is beneficial to produce the additive which is assumed to be produced in the manner described above, namely barium fluoride, whatever. For this purpose, such a zonal flavor may be the source of this material. For this purpose zenes BaF ₁ · RE, broken open and placed in a bridge, it can be placed in a graphite or platinum ship. Crucibles made of platinum and graphite are used. Bridgman - "" λ, "nmmv in a pin hydrogen fluoride atmosphere Crucibles are known to have a conical design in the lower area in one or more passes in a Ge so, whereby the tapering promotes the core speed of 1 to 10 per stand by the formation of single crystal growth will be processed, only heating device. The conical crucible is in a heavy platinum crucible most impurities have a distribution coefficient of approximately the same shape in an inert atmosphere, which is numerically less than 1, and the sphere or tightly packed in vacuum are concentrated in the end portion when solidifying. The crucible as well as the contents are at about 950 ^° C. The rod is broken off in order to remove this contaminated molten and upward (and normally discolored) section from the conical end. recrystallized at about 1 mm per hour After the zone-wise processing process only provides · Crystallization and before removal, the Hch is a process for removing impurities. and the material is tempered in order to relieve strains caused, for example, by water and hydrolysis stresses. During this period products, such as barium oxide and barium, the crystal will be at a temperature within about oxifluoride. If left at 200 ° C of the melting point for a few hours, these products produce inhomogeneities and, as a result, a light retention, after which it slowly diffuses to room temperature in the final crystal. Optionally, cooling (at a rate of about procedures include removal of moisture 65-25 ° C per hour which has been found suitable) at room temperature in a vacuum. For the use of the fluorescent material as a stimulant

AlIc liihandliingsvorgrinpf, bt-i ilimen «las biiiiimable medium become in an optical transmitter Fltunid the final composition on learning-favorably used single crystals. This was done in

Connection related to use in lasers with F i g. 3 explained. Single crystals can, however, also work together as a transformation layer be used with semiconductor diodes. A crystallization into a great product S of high perfection can be achieved by several methods.

The final waxing according to the Bridgman method yields a single crystal with dimensions on the order of 12.5 x 12.5 x 100 mm can be made using a horizontal zone process. Even bigger crystals can be grown using larger crucibles. These crystals are generally flawless, contain low levels of Er or Ho and are colorless, while crystals with higher contents of Er or Ho are slightly colored (Er - bL3-red; Ho - yellow) show. The crystals are hard and insoluble in waisers and can be optically polished will «· .. ao

The composition as well as the structure were based on wet chemical methods and X-ray structure analysis proven.

In the following examples, the general method of presentation explained above was followed, as for comparison purposes, according to the selected examples, all substances were melted by zone melting of powdered barium fluoride with an average particle size of 0.5 mm in a graphite ship in two passes at 3 cm per hour through a single induction heater manufactured. Under such conditions a zone length of 5 cm resulted. The zone melting process was carried out in an atmosphere of inert gas or hydrogen fluoride. The initial additives were all trifluorides and were prepared by reacting the trivalent ion, for example Yb ₁ O _3, with hydrogen fluoride at elevated temperature in the manner described above. This reaction was conducted in a graphite vessel within a platinum tube at temperatures of the order of 1000 ⁰ C. The reaction normally lasts one day, as has been proven by gravimetric analysis, and the trifluoride product obtained appeared as a white crystalline powder which was finally ^{melted at a temperature of about 1200 °} C. to form a solid mass.

The zone-wise melted BaF _a and the fluorides were then pulverized with a mortar and pestle. All additives were mixed intimately, placed in a graphite bowl and melted zone by zone in hydrogen fluoride at a rate of 1 cm per stand.

A final zone melt at a rate of about 0.3 cm pfo hour was ss carried out when a single crystal finished product should be obtained.

example 1 A compound according to the formula

BaY ₀₄ Yb ^ ₁ Er ₀₄ F ₅

became from the following according to the explained procedure Components manufactured:

BaF ₁ 17.53 g

YF ₁ 1.46g

YbF, it.lOg

FrF ₁ 2.21g

The connection achieved was applied to the emitting surface of a silicon-doped GaAs diode applied. A forward bias of 1.3 V resulted in a brightness of 53 820 asb ~ 2 sb. The emission takes place at 0.55 μm. The lighting efficiency was approximately the same as that of the GaP diode explained last.

Example 2

A compound according to the formula BaYb ₀ ,, Er _0. , F ₅

was produced in the manner described above with the following components:

BaF ₁ '17.53 g

YbF ₃ 20.70g

ErF ₃ 2.24g

Fine coating was produced in the manner described above. The diode was in Forward biased, resulting in an emission at 0.55 μm.

Example 3 The compound obtained corresponded to the formula

BaY ₀ . _e Yb _0il Er _0il F ₅ . The following components were used:

BaE, 17.53 g

11.68 g

YF ₃

YbF ₃

ErF ₃

2.30 g 2.24 g

A coating produced in the manner described above glowed brightly in green Area at a wavelength of 0J55 μιη under the Conditions according to example 1.

Example 4 The compound obtained corresponded to the formula

BaLu _0i5 Yb _0i45 Er ₀₁₅ F ₅ . The following components were used:

BaF ₁ 17.53 g

LuF ₁ 11.6 * »r,

YbF ₃ 10.35 g

ErF ₃ 1.12g

A coating and pre-tensioning as in Example 1 resulted in an emission at 0. SS pm.

Example 5 The compound obtained corresponded to the formula

BaY ₀₄ Yb ". _e Ho _Oll F ₅ . AI4 components were used:

BaF ₁ 17.53g

YF ₁ 1.46g

YbF, 18.4Og

HoF ₃ 2.22g

Irradiation with a silicon-doped GaAs diode resulted in a bright green emission from a Wavy line of 0.51; in

Z OiS 352

Example 6 The «Veibmdimg aimed, matched the formula

AIs components were used:

BaCI ₁ 20.82g

9.76g

12 ^ 7g

_t 1.37 g

In a doped Süizhiin and m in the manner described above-J ^ Voig "panniert GaAs Sode throws after humidification" ne bright Ro * emisaon including a wavelength of 0.66 μιη loading

^ Egpn Examples & ** ^ ££
large Versochsreihe at which -Teischiedene amendments to the composition rmesn both in terms of Xe ds and the nature of the substances carried out JJ ^ _The aDgemein combined F ™ ^{1 50} J "* ⁵ *» besSbenen various areas has been on S the observations on the entire test series derived.

1 sheet of drawings

Claims (5)

* 2 j i have, for example, a forward-biased semiconductor diode with a pn junction. These diodes essentially consist 1. Up-transforming fluorescent luminescent aas gallium phosphide, which is used to adjust the g material for converting infrared radiation into 5 desired wavelengths of the resulting radiation ϊ visible radiation, which is essentially made up of doped with various substances. Such a one } Alkaline earth halide consists of ytterbium in addition to in the red wavelength range with an efficiency Contains holmium or erbium, characterized is overall of 3.4 ° / ₀ emittii-emitting diode in nevertheless meeting j indicates that the alkaline earth halide report No. 610 by I. Ladany of the »Electro- material approximately according to the formula "Chemical Society Meeting" in Montreal, October 11th 1968, described. Ba (M _x RE ₁ , Yb ₁ - * - ,,) ,, X _{1 + 3} . It is also known (conference report No. 2 "Spontane Emission" by SV Galginait, among others, which is composed of M at least one "International Conference of GaAs" in Dallas, j element from the group consisting of Y, Lu, Gd, 15 17 October 1968), as electroluminescent devices Ce, Sc, La, Ga, In and Al; RE at least one signal in the infrared wavelength range. emissi- ■ element from the group consisting of Er as well as rende GaAs diodes to be used, which are used for trans-Ho; and X represent at least one halogen; and formation of the infra-radiation into radiation in the where χ in the range from 0 to 0.95, y a visible range a so-called up to range from 0.01 to 0.3 and χ a range of ao-converting fluorescent coating. Can run under 0.05 to 4. the concept of an "upward conversion" becomes a 2. Fluorescent substance according to claim 1, characterized in that the frequency transformation in the direction of higher frequency is understood in that the element Er and radiation are understood for RE. This coating, whose element F is used for X and that χ According to current opinion, the mode of action is based on two photon processes taking place in a range of values from 0 to 0.82, y contains from 0.03 to 0.2 and χ from 0.4 to 3 as fluorescence embedding material include lanthanum fluoride. (LaF ₃ ), which with a ytterbium (Yb ^3f ) -Sensibili- 3. fluorescent substance according to claim 2, characterized by satorion and an erbium (Er ^ Aktivatorion ve-characterized, that M corresponds to element Y is impure. A disadvantage of such GaAs diodes and a comprises a range from 0.6 to 1.5. However, it is the poor efficiency that is essential 4. fluorescent substance according to claim 3, characterized in that it is lower than that of good GaP diodes. characterized in that χ is equal to 1 ± 10 ° / ₀ . It is still from those working in the infrared 5. Light converter with a. Fluorescent luminous quantum counters known (magazine "Applied Optics", material according to claim 1, characterized, Vol. 7, No. 10, October 1968, pp. 2053 to 2070), Erddaß this fluorescent phosphor as a layer (8) 35 alkali halides in cooperation with Ytterbium, the radiation-emitting surface of a GaAs to use alongside holmium or erbium.
Covered light emitting diode. The known lasers provide coherent light sources