WO2014092314A1

WO2014092314A1 - Encapsulation composition and encapsulated device comprising same

Info

Publication number: WO2014092314A1
Application number: PCT/KR2013/008778
Authority: WO
Inventors: 하경진; 권지혜; 오세일; 이연수; 이창민; 최승집
Original assignee: 제일모직 주식회사
Priority date: 2012-12-12
Filing date: 2013-10-01
Publication date: 2014-06-19
Also published as: KR20140076423A; KR101616159B1

Abstract

The present invention relates to an encapsulation composition which comprises a light-curing mixture and an initiator, wherein the light-curing mixture comprises between about 40 and 100 percent by weight of a di(meth)acrylate monomer of formula 1 or an oligomer thereof, and the present invention also relates to an encapsulated device comprising the encapsulation composition.

Description

Composition for encapsulation and encapsulated device comprising same

The present invention relates to a composition for encapsulation and an encapsulated device comprising the same.

Organic optoelectronic devices such as organic light emitting diodes, devices comprising photovoltaic cells and display devices such as organic thin film transistors must be encapsulated to protect their sensitive components from gases and / or moisture such as oxygen in the atmosphere. Without proper protection, the quality of the display device may be degraded. In addition, deterioration of the quality of the display device may appear due to the occurrence of mainly dark non-radioactive spots. In particular, the organic light emitting diode display device may be degraded due to water vapor penetrating into the organic light emitting diode, and may degrade the quality of the cathode (or anode) / organic membrane interface.

It is an object of the present invention to provide a composition for encapsulation capable of forming a barrier layer for encapsulation of an environmentally sensitive device member.

Another object of the present invention is to provide a composition for encapsulation that can implement a barrier layer having low shrinkage and storage modulus after curing, high hardness, low chlorine ion content, high surface energy, and low outgas generation.

Still another object of the present invention is to provide a composition for encapsulation, which has high adhesion to the inorganic barrier layer and can enhance the complementary effect of the inorganic barrier layer.

It is another object of the present invention to provide a composition for encapsulation that can form a barrier layer with low permeability of oxygen and / or water vapor and / or moisture and / or chemicals.

Still another object of the present invention is to provide an encapsulated device comprising the composition for encapsulation.

The composition for encapsulation of the present invention includes a photocurable mixture and an initiator, and the photocurable mixture may include about 40 to 100% by weight of the di (meth) acrylate monomer or the oligomer thereof of Formula 1 in the photocurable mixture. Can:

(In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Z ₁ , Z ₂ are as defined in the following detailed description).

The encapsulation composition of the present invention has a shrinkage after curing of about 10% or less, a storage modulus after curing of about 200 MPa-2000 MPa, a hardness of about 50 MPa-100 MPa after curing, and a chlorine ion content of about 10 ppm or less after curing, and curing The surface energy is about 30 mN / m or more, and may include the di (meth) acrylate monomer or an oligomer thereof.

An encapsulated device of the invention comprises a device member; And a barrier stack formed on the device member, the barrier stack including an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer may be formed of the encapsulation composition.

The present invention can form a barrier layer for encapsulation of an environmentally sensitive display device, can form a barrier layer with low permeability of oxygen and / or water vapor and / or moisture and / or chemicals, The present invention provides a composition for encapsulation and an encapsulated device including the same, which can implement a barrier layer having high adhesion to the inorganic barrier layer and having a complementary effect with an inorganic barrier layer.

1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.

2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

In the present specification, "upper" and "lower" are defined based on the drawings, and according to the viewing time, "upper" may be changed to "lower" and "lower" to "upper", and in "substituted or unsubstituted""Substituted" means that at least one hydrogen atom of the functional group of the present invention is halogen (F, Cl, Br or I), hydroxy group, nitro group, cyano group, imino group (= NH, = NR, R is an alkyl group having 1-10 carbon atoms) ), Amino group (-NH ₂ , -NH (R '), -N (R ") (R"'), R ', R ", R"' are each independently an alkyl group having 1 to 10 carbon atoms), carbon number Substituted with an alkyl group of 1-20, an aryl group having 6-20 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, a heteroaryl group having 3-20 carbon atoms, a heterocycloalkyl group having 2-30 carbon atoms, an arylalkyl group having 7-21 carbon atoms "Cycloalkyl group" means an aliphatic cyclic hydrocarbon having 3-10 carbon atoms, preferably an aliphatic cyclic hydrocarbon having 5-10 carbon atoms, more preferably an aliphatic ring having 5-6 carbon atoms Type hydrocarbon, most preferably cyclohexyl group, 'aryl group' means an aromatic group having 6 to 20 carbon atoms, preferably an aromatic group having 6 to 10 carbon atoms, most preferably a phenyl group, and an 'arylalkyl group 'Is an alkyl group containing an aryl group having 7 to 21 carbon atoms, preferably an alkyl group containing an aryl group having 7 to 11 carbon atoms, more preferably a benzyl group, and an' alkoxy group 'is a hydrocarbon group having 1 to 10 carbon atoms containing oxygen, preferably Preferably it means an oxygen-containing hydrocarbon group of 1 to 5 carbon atoms, more preferably a methoxy group or an ethoxy group, 'oligomer' may mean a polymer polymerized with the monomer, wherein the polymerization is a polymerization commonly known to those skilled in the art ( (E.g., solution polymerization, suspension polymerization, interfacial polymerization, etc.), '*' means inter-linking site, and '(meth) acrylate' means acrylate and / or methacrylate.

Hereinafter, the composition for sealing of one embodiment of the present invention will be described in more detail.

The composition for encapsulation of an embodiment of the present invention comprises a photocurable mixture and an initiator, wherein the photocurable mixture comprises about 40 to 100% by weight of a di (meth) acrylate monomer or an oligomer thereof of Formula 1 Can include:

(In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are independently of each other hydrogen, halogen, hydroxy group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted. An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms, At least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or substituted or Unsubstituted arylalkyl group having 7 to 21 carbon atoms,

Z ₁ and Z ₂ are each independently the following Chemical Formula 2a or Chemical Formula 2b.

(In Formulas 2a and 2b, * is a linking site, R ₃₀ is hydrogen or a methyl group, Y is a substituted or unsubstituted C 1-20 alkylene group, a substituted or unsubstituted C 6-20 arylene group, A substituted or unsubstituted arylalkylene group having 7 to 21 carbon atoms, or a substituted or unsubstituted alkyleneoxy group having 1 to 20 carbon atoms, n is an integer of 1 to 20).

The di (meth) acrylate monomer is a silicon-free non-silicone photocurable monomer, which lowers the cure shrinkage rate of the encapsulation composition, increases surface energy after curing of the encapsulation composition, and increases adhesion to the inorganic barrier layer. After curing, the hardness and storage modulus can be lowered to increase the encapsulation efficiency of the barrier stack.

For example, R ₁ is a substituted or unsubstituted cycloalkyl group having 3-10 carbon atoms or a substituted or unsubstituted aryl group having 6-20 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are Independently of each other, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and Y may be a linear or branched alkylene group having 1 to 5 carbon atoms.

The di (meth) acrylate monomer or oligomer thereof may have a weight average molecular weight of about 50-1000 g / mol, for example, about 300-600 g / mol, and in the above range, the deposition characteristics may have an excellent effect.

The di (meth) acrylate monomer or oligomer thereof may be included in about 40 to 100% by weight, such as 100% by weight or about 50 to 99.99% by weight or about 40 to 80% by weight, based on solids in the photocurable mixture, Within this range, it is possible to lower the curing shrinkage rate, increase the adhesion to the inorganic barrier layer after curing, and lower the hardness and storage modulus.

Di (meth) acrylate monomers or oligomers thereof can be synthesized by conventional methods known to those skilled in the art.

The initiator may include, without limitation, conventional photopolymerization initiators capable of carrying out the photocurable reaction. For example, the photopolymerization initiator may include phosphorus, acetophenone, triazine, benzophenone, thioxanthone, benzoin, oxime or mixtures thereof. Preferably, phosphorus or acetophenone series can be used. Specifically, the acetophenone system is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) -1-butanone, or a mixture thereof, and the phosphorus system may be trimethyl benzoyldiphenyl phosphine oxide, or a mixture thereof.

The initiator may be included in more than about 0 to 2 parts by weight, for example about 0.01 to 2 parts by weight, for example about 1 to 2 parts by weight, based on 100 parts by weight of the photocurable mixture, based on the solid content of the encapsulation composition. Photopolymerization can sufficiently occur in the range, the transmittance can be prevented from being lowered due to the remaining unreacted initiator, and the amount of outgas generated can be reduced.

The composition for encapsulation of another embodiment of the present invention includes a photocurable mixture and an initiator, and the photocurable mixture includes about 50 to 99.99% by weight of the di (meth) acrylate monomer or its oligomer of Formula 1 in the photocurable mixture. And a silicone (meth) acrylate monomer or oligomer thereof having at least one of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted alkoxy group. It may further comprise one or more of a silicone (meth) acrylate monomer or an oligomer thereof. It is substantially the same as the encapsulation composition of an embodiment of the present invention except that it further comprises a silicone (meth) acrylate monomer or an oligomer thereof. Hereinafter, a silicone (meth) acrylate monomer or its oligomer is demonstrated in detail.

The silicone (meth) acrylate monomer or oligomer thereof having at least one of a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl group may be represented by the following Formula 3:

(In Formula 3, R ₁₁ , R ₁₂ , and R ₁₃ are each independently hydrogen, halogen, hydroxy group, substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C3-10 cycloalkyl group, A substituted or unsubstituted aryl group having 6-20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7-21 carbon atoms, at least one of R ₁₁ , R ₁₂ , and R ₁₃ has 3-10 unsubstituted or substituted carbon atoms Is a cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms, Z ₁ is as defined above.

Silicone (meth) acrylate monomers or oligomers thereof may be included in the composition for encapsulation to lower the curing shrinkage rate and storage modulus and to implement a good adhesion effect with the inorganic layer.

Specifically, R ₁₁ is a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms, R ₁₂ , R ₁₃ may be an independently substituted or unsubstituted alkyl group having 1-5 carbon atoms.

The silicone (meth) acrylate monomer or oligomer thereof may have a weight average molecular weight of about 50-1000 g / mol, for example, about 50-500 g / mol, and in the above range, may have an effect of improving adhesion.

Silicone (meth) acrylate monomers or oligomers thereof may be included in about 0.01-50% by weight or about 10-50% by weight in the photocuring mixture on a solids basis, in the above range, may have an effect of improving adhesion.

The silicone (meth) acrylate monomer having a substituted or unsubstituted alkoxy group may be represented by the following general formula (4):

(In Formula 4, R ₂₁ , R ₂₂ , and R ₂₃ are independently of each other hydrogen, halogen, hydroxy group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. And at least one of R ₂₁ , R ₂₂ , and R ₂₃ is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and Z ₁ is as defined above.

The silicone (meth) acrylate monomers or oligomers thereof may be included in the encapsulation composition to lower the curing shrinkage rate and storage modulus and to implement a good adhesion effect with the inorganic layer.

For example, R ₂₁ , R ₂₂ , and R ₂₃ are independently substituted or unsubstituted alkoxy groups having 1 to 5 carbon atoms, and the silicone (meth) acrylate monomer may be a trialkoxy silicone (meth) acrylate monomer. have.

The silicone (meth) acrylate monomer or oligomer thereof may have a weight average molecular weight of about 50-500 g / mol, for example about 100-300 g / mol. In the above range, there may be an excellent adhesion effect with the inorganic barrier layer.

The silicone (meth) acrylate monomer or oligomer thereof may be included in about 0.01-50% or about 10-50% by weight of the photocurable mixture. In the above range, there may be an effect of improving the adhesion.

Silicone (meth) acrylate monomers or oligomers thereof may be synthesized or purchased as a commodity by conventional methods known to those skilled in the art.

In one embodiment, the photocurable mixture may comprise 100% by weight of a di (meth) acrylate monomer or oligomer thereof. In another embodiment, the photocurable mixture may comprise about 50-99.99% by weight of the di (meth) acrylate monomer or oligomer thereof, and about 0.01-50% by weight of the monomer of Formula 3 or oligomer thereof. In another embodiment, the photocurable mixture may comprise about 50-99.99% by weight of the di (meth) acrylate monomer or oligomer thereof and about 0.01-50% by weight of the monomer or oligomer of Formula 4. In another embodiment, the photocurable mixture comprises about 40-80% by weight of a di (meth) acrylate monomer or oligomer thereof, about 10-50% by weight of the monomer of Formula 3 or an oligomer thereof, and about about monomer of the monomer of Formula 4 or an oligomer thereof It may comprise 10-50% by weight.

The composition for encapsulation of another embodiment of the present invention may further include a photocurable monomer having one or more photocurable functional groups (eg, vinyl groups or (meth) acrylate groups). For example, the photocurable monomer may be a (meth) acrylate or di (meth) acrylate of a straight chain, branched or cyclic saturated hydrocarbon. Specifically, the photocuring monomer may be at least one of saturated C 5-20 polyalcohol di (meth) acrylate, more specifically dodecanediol di (meth) acrylate and nonanediol di (meth) acrylate. Can be. The photocurable monomer may be included in less than about 40% by weight of the photocurable mixture. In the above range, it can implement the physical properties of the composition for encapsulation to be described below. For example, about 0-20% by weight of the photocurable mixture, for example about 0.0001-20% by weight.

The composition for sealing can be formed by mixing a photocurable mixture and an initiator. Preferably, it can be formed in a solventless type.

The composition for encapsulation of another embodiment of the present invention may further include an antioxidant (heat stabilizer). Antioxidants can improve the thermal stability of the encapsulation layer. The antioxidant may include, but is not limited to, one or more selected from the group consisting of phenolic, quinone, amine and phosphite based. For example, the antioxidant may be tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane or tris (2,4-di-tert-butylphenyl) phosphite It may contain the above.

The antioxidant may be included in an amount of about 0.01-3 parts by weight, preferably about 0.01-1 part by weight, based on 100 parts by weight of the photocurable mixture. In the above range, it is possible to prevent the aging of the film after curing, and exhibit excellent thermal stability.

In one embodiment, the encapsulation composition may comprise about 95-99% by weight of the photocurable mixture and about 1-5% by weight of the initiator and antioxidant on a solids basis. In the above range, excellent thin film encapsulation is possible, and photocuring efficiency may be good. Preferably, about 97-99% by weight of the photocurable mixture and about 1-3% by weight of the sum of the initiator and the antioxidant may be included.

In one embodiment, the encapsulation composition may comprise about 90-99 weight percent of di (meth) acrylate monomer or oligomer thereof, about 0.01-5 weight percent of initiator, and about 0.01-5 weight percent of antioxidant on a solids basis have.

In another embodiment, the encapsulation composition comprises about 45-80% by weight of the di (meth) acrylate monomer or oligomer thereof, about 15-50% by weight of the monomer of Formula 3 or oligomer, about 0.01-5% by weight of the initiator, based on solids , And about 0.01-5% by weight antioxidant.

In another embodiment, the encapsulation composition comprises about 45-80% by weight of the di (meth) acrylate monomer or oligomer thereof, about 15-50% by weight of the monomer of Formula 4 or oligomer thereof, and about 0.01-5% of the initiator by solid content %, And about 0.01-5% by weight antioxidant.

In another embodiment, the encapsulation composition comprises about 35-80% by weight of the di (meth) acrylate monomer or oligomer thereof, about 5-30% by weight of the monomer of Formula 3 or oligomer thereof, monomers of Formula 4 or About 5-30% oligomer, about 0.01-5% initiator, and about 0.01-5% antioxidant.

The encapsulation composition may have a curing shrinkage of about 10% or less. In the above range, by minimizing the stress generated during photocuring, it is possible to suppress the pin-hole generation by minimizing the stress on the inorganic barrier layer deposited when forming the barrier stack. If the shrinkage rate after curing is greater than about 10%, the smoothing property is poor due to the shrinkage of the organic layer formed of the photocured encapsulating composition, which causes defects to occur during the deposition of the inorganic barrier layer, thereby resulting in moisture permeability (WVTR, water). The vapor transmission rate may be poor, and the display member (eg, the organic light emitting diode) may not emit light due to the infiltrated oxygen and / or moisture, thereby increasing the possibility of dark spots. For example, the cure shrinkage may be about 0.01-10%, for example about 3.0-6.5%. Hardening shrinkage can be measured with reference to the following experimental example.

The composition for encapsulation may have a storage modulus of about 200 MPa-2,000 MPa after curing. In the above range, by minimizing the stress generated during photocuring, it is possible to suppress the generation of pinholes by minimizing the stress on the inorganic barrier layer deposited when forming the barrier stack. For example, about 200 MPa-1,150 MPa, for example, about 600 MPa-1,150 MPa. After curing, storage modulus can be measured with reference to the following experimental examples.

The composition for encapsulation may have a hardness after curing of about 100 MPa or less, for example about 50 MPa-100 MPa, for example 60 MPa-95 MPa. In the above range, the deposition of the inorganic barrier layer can be facilitated to facilitate the formation of the barrier stack. When the hardness is greater than 100 MPa, adhesion characteristics may not be smooth when the inorganic barrier layer is deposited, and thus the smooth inorganic barrier layer may be poorly formed. When the hardness is less than 50MPa, the inorganic material for forming the inorganic layer penetrates into the composition for encapsulation of the organic barrier layer, thereby hindering the formation of a smooth inorganic barrier layer, which may result in poor sealing properties. Hardness can be measured with reference to the following experimental example.

The composition for encapsulation may have a chlorine ion content of about 10 ppm or less. Chlorine ions are generated during the preparation of the monomer or oligomer thereof included in the composition for encapsulation, and are difficult to remove even after several purification. The encapsulation composition of the present invention has a chlorine ion content of 10 ppm or less, thereby preventing corrosion of electrodes of a display device (for example, an organic light emitting device), thereby suppressing dark spots easily generated from poor reliability. If the chlorine ion content is more than 10 ppm, corrosion of the cathode material of the display device can easily occur. For example, the chlorine ion content may be about 0-10 ppm, for example about 0-5 ppm, for example about 0 ppm. Chlorine ion content can be measured with reference to the following experimental example.

The sealing composition may have a surface energy of about 30 mN / m or more after curing. In the above range, it is possible to increase the adhesion with the inorganic barrier layer deposited on the organic barrier layer when the barrier stack is formed. For example, about 30-50 mN / m, for example about 30-42 mN / m. Surface energy can be measured with reference to the following experimental example.

The sealing composition may have a transmittance of about 95% or more after curing. Within this range, the visibility of the display device can be improved when the display device is encapsulated. The transmittance is the value measured at wavelength 480nm-680nm, for example, wavelength 550nm. Preferably, it may be about 95-100%. The transmittance can be measured with reference to the following experimental example, but is not limited thereto.

The composition for encapsulation may be about 200 ppm or less after generation of outgas after curing. The outgas may be derived from an initiator or photocurable resin included in the composition for encapsulation. In the above range, when applied to the display device is insignificant, the life of the display device can be extended. For example, about 10-200 ppm, for example about 100-200 ppm, for example about 100-185 ppm. Outgassing after curing can be measured with reference to the following experimental example.

The composition for encapsulation may have a curing rate of about 95% or more. In the above range, the hardening shrinkage stress after curing is implemented to implement a layer that does not generate a shift can be used for the sealing of the display device. For example, about 95-100%. Curing rate can be measured with reference to the following experimental example.

The composition for encapsulation may have a moisture permeability (WVTR) of about 10 ⁻⁶ g / m ² · day or less, for example about 10 ⁻⁸ to 10 ⁻⁶ g / m ² · day, in the thickness direction after curing. Moisture permeability can be measured with reference to the following experimental example.

On the other hand, device members, in particular display device members, are decomposed or defective due to permeation of gases or liquids in the surrounding environment, such as oxygen and / or moisture in the atmosphere and / or water vapor and chemicals used in processing electronics. Can be. For this purpose the device element, in particular the display device, needs to be encapsulated or encapsulated.

Members for such devices include organic light emitting devices, lighting devices, flexible organic light emitting device displays, metal sensor pads, microdisk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits, charge coupling Devices, light emitting polymers, light emitting diodes, and the like, but is not limited thereto.

The composition for encapsulation of the present invention satisfies at least one of the above-mentioned post-curing shrinkage, storage modulus, hardness, chlorine ion content, surface energy, transmittance, outgas generation amount, and curing rate, thereby encapsulating or encapsulating the member for the device. The organic barrier layer used can be formed.

The organic barrier layer of the present invention may be formed of the encapsulation composition of the embodiments of the present invention.

The organic barrier layer can be formed by photocuring the composition for sealing. Although not limited, the encapsulation composition can be coated to a thickness of about 0.1 μm-20 μm and cured by irradiation at about 10-500 mW / cm ² for about 1-50 seconds.

The organic barrier layer has the physical properties of the composition for encapsulation after curing described above. Therefore, the barrier stack may be formed together with the inorganic barrier layer to be described below, and may be used for encapsulation of the display device.

A barrier stack, which is another aspect of the present invention, may include the organic barrier layer and the inorganic barrier layer.

The inorganic barrier layer may be formed of an inorganic layer different from the organic barrier layer, thereby supplementing the effect of the organic barrier layer.

The inorganic barrier layer is not particularly limited, but may be a metal, a nonmetal, an oxide thereof, a nitride thereof, a carbide thereof, an oxygen nitride thereof, an oxygen boride compound thereof, or a mixture thereof. The metal or nonmetal may be silicon (Si), selenium (Se), zinc (Zn), antimony (Sb), aluminum (Al), transition metal, lanthanide metal, indium (In), germanium (Ge), tin (Sn). ), Bismuth (Bi), or a combination thereof, but is not limited thereto. Specifically, SiOx, SiNx, SiOxNy, ZnSe, ZnO, Sb ₂ O ₃ , Al ₂ O ₃ , In ₂ O ₃ , SnO _2, etc. (wherein x is 1 to 5 and y is 1-). 5).

The inorganic barrier layer and the organic barrier layer may be deposited in a vacuum process, such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and combinations thereof.

The organic barrier layer secures the above-described physical properties. As a result, when the organic barrier layer is deposited alternately with the inorganic barrier layer, it is possible to secure the smoothing characteristics of the inorganic barrier layer. In addition, the organic barrier layer can prevent the defect of the inorganic barrier layer from propagating to another inorganic barrier layer.

The barrier stack includes the organic barrier layer and the inorganic barrier layer, but the number of barrier stacks is not limited. The combination of barrier stacks may vary depending on the level of permeation resistance to oxygen and / or moisture and / or water vapor and / or chemicals.

In the barrier stack, the organic barrier layer and the inorganic barrier layer may be deposited alternately. This is because of the effect on the barrier layer of the organic barrier layer produced due to the physical properties of the composition for encapsulation described above. As a result, the effects on the display device generated from the organic barrier layer and the inorganic barrier layer can be supplemented or enhanced.

1 illustrates a structure in which an organic barrier layer 32 and an inorganic barrier layer 31 are deposited in the barrier stack 30. Preferably, the organic barrier layer and the inorganic barrier layer can be deposited alternately in a plurality of times, more preferably the inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic It may be formed of a seven-layer structure of the barrier layer.

The thickness of the barrier stack is not limited, but may be about 1.5 μm-5 μm.

In the barrier stack, the thickness of one organic barrier layer may be about 0.1 μm-20 μm, preferably 1 μm-10 μm, and the thickness of one inorganic barrier layer may be about 5 nm-500 nm, preferably about 5 nm-200 nm. .

The barrier stack is a thin film encapsulant and may have a thickness of about 5 μm or less, preferably about 1.5 μm-5 μm.

Another aspect of the invention is an encapsulated device comprising a member for a device; And a barrier stack formed over the device member, the barrier stack comprising an inorganic barrier layer and an organic barrier layer, wherein the organic barrier layer may be formed of the composition.

1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention. Referring to FIG. 1, the encapsulated device 100 includes a substrate 10; A device member 20 formed on the substrate 10; And a barrier stack 30 formed on top of the device member 20 and composed of an inorganic barrier layer 31 and an organic barrier layer 32, wherein the device member 20 includes an inorganic barrier layer 31. Contact with

2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention. 2, the encapsulated device 200 includes a substrate 10; A device member 20 formed on the substrate 10; And a barrier stack 30 formed on top of the device member 20 and composed of an inorganic barrier layer 31 and an organic barrier layer 32, wherein the device member 20 includes an inorganic barrier layer 31. The inorganic barrier layer 31 may encapsulate the internal space 40 in which the device member 20 is accommodated.

The contents for the device member, the organic barrier layer, the inorganic barrier layer, and the barrier stack are as described above.

The organic barrier layer may have a storage modulus of about 200 MPa-2000 MPa, a hardness of about 50 MPa-100 MPa, and a surface energy of about 30 mN / m or more.

The organic barrier layer may include a cured product of the encapsulation composition.

The substrate is not particularly limited as long as it is a substrate on which device members can be laminated. For example, it may be made of a material such as transparent glass, plastic sheet, silicon or metal substrate.

The encapsulated device can be manufactured by conventional methods. A device member is deposited on the substrate and an inorganic barrier layer is deposited. The composition for sealing can be apply | coated using methods, such as spin coating and a slit coating, and can be irradiated with light to form an organic barrier layer. The process of forming the inorganic barrier layer and the organic barrier layer can be repeated (preferably up to about 10 times in total, more preferably up to 7 times in total, 2-10 times, 2-7 times).

Another aspect of the invention, the method of encapsulating the device may comprise the following steps:

Positioning or stacking one or more device members adjacent to the substrate; And

Depositing at least one barrier layer comprising at least one inorganic barrier layer and an organic barrier layer and adjacent the device component.

Details of the substrate, the device member, the inorganic barrier layer, the organic barrier layer, and the barrier stack are as described above.

The device member is positioned or laminated to the substrate adjacent to the device. This can be carried out in the same manner as the inorganic barrier layer and organic barrier layer deposition method, but is not limited thereto.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) photocuring mixture

(A1) Monomer of Formula 1a

<Formula 1a> (SM-1100, SM Korea)

(A2) Monomer of Formula 3a

<Formula 3a> (3-SPA, Cheil Industries)

In a four-necked flask under N ₂ atmosphere, 500 g of chloroform, 1 mol (206,74 g) of 3- (chlorodimethylsilyl) propyl acrylate, and 1 mol (72 g) of Benzene were synthesized at room temperature for 4 hours using 300 ppm of catalyst Triethylamine, and then purified and purified by 80%. The above monomer (3-SPA) was synthesized.

(A3) Monomers of the general formula (4a)

<Formula 4a> (KBM-503, shinetsu silicone (日))

(B) Initiator: (B1) diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, (B2) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-buta Rice fields (Irgacure 369)

(C) Antioxidant: Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

(D) di (meth) acrylate of straight chain saturated hydrocarbon: (D1) dodecanediol diacrylate (DDA), (D2) nonanediol diacrylate (NDA)

실시예 1 내지 9와 비교예 1 내지 8Examples 1-9 and Comparative Examples 1-8

The components (A), (B), (C) and (D) described above are mixed in the contents (unit: parts by weight) described in Tables 1 and 2 below, and mixed for 3 hours using a shaker to form a composition for encapsulation Was prepared.

Table 1

		Example
		One	2	3	4	5	6	7	8	9
(A)	(A1)	100	50	50	80	80	80	40	100	40
	(A2)	-	50	-	10	20	-	30	-	30
	(A3)	-	-	50	10	-	20	30	-	30
(D)	(D1)	-	-	-	-	-	-	-	-	-
(D)	(D2)	-	-	-	-	-	-	-	-	-
(B)	(B1)	One	One	One	One	One	One	One	One	One
(B)	(B2)	-	-	-	-	-	-	-	One	One
(C)		0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1

TABLE 2

		Comparative example
		One	2	3	4	5	6	7	8
(A)	(A1)	39	39	-	-	-	-	-	-
	(A2)	-	-	60	60	-	-	-	-
	(A3)	-	-	-	-	60	60	-	-
(D)	(D1)	61	-	40	-	40	-	100	-
(D)	(D2)	-	61	-	40	-	40	-	100
(B)	(B1)	One	One	One	One	One	One	One	One
(B)	(B2)	-	-	-	-	-	-	-	-
(C)		0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1

The physical properties of the encapsulation compositions prepared in Examples and Comparative Examples were evaluated, and the results are shown in Tables 4-5 below.

Property evaluation method

1. Hardening shrinkage (%): The hardening shrinkage was calculated by measuring the specific gravity of the liquid composition before photocuring and the specific gravity of the solid after curing with DME-220E (Shinko, Japan). The composition was coated with a thickness of 10 μm ± 2 μm, followed by UV curing (100 mW / cm ² X 10 seconds) to prepare a film (thickness: 8 to 12 μm, width 1.5 to 2.5 cm, length 1.5 to 2.5 cm). The cure shrinkage rate can be calculated according to the following formula (1).

Cure Shrinkage (%) = [(Solid specific gravity after curing-specific gravity of liquid composition before curing)] / Specific gravity of liquid composition before curing x 100

2. Storage modulus (MPa): After coating the composition on a clean glass substrate, the amount of light was irradiated at 2000 mJ / cm ² to cure around 500 μm in thickness and 25 mm in diameter to make a film. With ARES, model name ARES-G2 (TAinstrument), the frequency was measured at a rate of 10 ° C./min from 25 ° C. to 100 ° C. under a condition of 1 rad / s and a strain of 0.01%, and at 25 ° C. Measure the value of.

3. Hardness (MPa): The composition was coated on a clean glass substrate to a thickness of about 10 μm ± 2 μm and then UV cured (100 mW / cm 2 x 10 seconds) to prepare a film (thickness: 1 to 3 μm). . The hardness of the prepared film was measured using a nanointender (Hysitron TI750 by Hysitron). At the top of the film was applied for 5 seconds at a height of 100nm to give a maximum load of 250μN and then measured for 2 seconds after holding for 2 seconds.

4. Chlorine ion content (ppm): A certain amount (1 ~ 50mg) of the composition for encapsulation is weighed and transferred to a boat, and then mounted on an autosampler. Analyze after confirming the conditions in the automatic combustion device such as Absorption Solvent and Rinse. The combustion apparatus used was AQF-2100H (Mitsubishi Chemical Co.), and the ion chromatography used IC-5000S (DIONEX).

5.Surface energy (mN / m): The composition was coated on a clean glass substrate to about 10 μm ± 2 μm and then UV cured (100 mW / cm ² × 10 seconds) to prepare a film (thickness: 9 μm ± 2 μm). It was. Distilled water was dropped on the film at 25 ° C., and the contact angle between the distilled water and the film was measured, and the surface energy was calculated. The equipment used was SEO 300A model SEO Co.

6. Out gas generation amount (ppm): After coating the composition to a thickness of 10㎛ ± 2㎛ on the cleaned glass substrate and UV curing (100mW / cm ² X 10 seconds) to prepare a film (thickness: 9㎛ ± 2㎛) It was. The outgas was collected by Pyrolyzer GC-MS and measured.

Specifically, the photocurable composition was sprayed onto the glass substrate and irradiated with 100 mW / cm ² for 10 seconds to UV cured to obtain an organic barrier layer specimen of 20 cm x 20 cm x 3 μm (width x length x thickness). For specimens, use a GC / MS instrument (Perkin Elmer Clarus 600). GC / MS uses a DB-5MS column (length: 30 m, diameter: 0.25 mm, fixed bed thickness: 0.25 μm) as a column, and helium gas (flow rate: 1.0 mL / min, average velocity = 32 cm / s) as a mobile phase. The split ratio is 20: 1, and the temperature condition is maintained at 40 ° C. for 3 minutes, and then the temperature is raised at a rate of 10 ° C./minute, and then maintained at 320 ° C. for 6 minutes. Out size is glass size 20cm x 20cm, collection vessel is Tedlar bag, collection temperature is 90 ℃, collection time is 30 minutes, N ₂ purge flow rate is 300mL / min, adsorbent is Tenax GR (5% phenylmethylpolysiloxane) ) To capture. As a standard solution, a calibration curve is prepared with 150 ppm, 400 ppm, and 800 ppm of toluene solution in n-hexane, and an R2 value of 0.9987 is obtained. The above conditions are summarized in Table 3 below.

TABLE 3

division		Detail
Collection conditions		Glass size: 20cm X 20cm
		Collection Container: Tedlar bag
		Collection temperature: 90 ℃
		Capture time: 30 min
		N ₂ purge flow rate: 300 mL / min
		Adsorbent: Tenax GR (5% phenylmethylpolysiloxane)
Calibration curve creation condition		Standard Solution: Toluene in n-Hexane
		Reference range: 150 ppm, 400 ppm, 800 ppm
		R2: 0.9987
GC / MS condition	Column	DB-5MS → 30m x 0.25mm x 0.25㎛ (5% phenylmethylpolysiloxane)
	Mobile phase	He
	Flow	1.0 mL / min (Average velocity = 32 cm / s)
	Split	Split ratio = 20: 1
	method	40 ° C (3 min) → 10 ° C / min → 320 ° C (6 min)

7. Curing rate (%): the intensity of the absorption peak in the FT-IR (NICOLET 4700, Thermo Co.) for use in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 vicinity (C = O) with respect to the composition Measure The composition is coated on and around 10 μm ± 2 μm on a glass substrate and UV cured at 100 mW / cm ² for 10 seconds to obtain a 20 cm x 20 cm x 3 μm (width x length x thickness) specimen. Obtain a cured film and, FT-IR (NICOLET 4700, Thermo Co.) is used in the vicinity of 1635cm ^-1 (C = C), 1720cm ^-1 measured intensity of the absorption peak in the vicinity of the (C = O) a. Curing rate is computed according to following formula (2).

Curing Rate (%) = | 1- (A / B) | x 100

(A above, A is the ratio of the intensity of the absorption peak in the vicinity of 1635 cm ⁻¹ to the intensity of the absorption peak in the vicinity of 1720 cm ⁻¹ for the cured film,

B is the ratio of the intensity of the absorption peak at around 1635 cm ⁻¹ to the intensity of the absorption peak at around 1720 cm ⁻¹ for the composition)

8. Transmittance: The composition was coated on the cleaned glass substrate to a thickness of about 10 μm ± 2 μm and then UV cured (100 mW / cm ² × 10 sec) to prepare a film (thickness: 9 μm ± 2 μm). Visible light transmittance in the wavelength range of 550 nm was measured with a Lambda 950 (Perkin elmer) instrument for the prepared film.

9. Moisture permeability: After coating the composition on the glass substrate with a spray thickness of 5㎛, UV cured (100J / cm ² ) for 10 seconds to cure the cured specimen (organic barrier layer, thickness 5㎛) moisture permeability meter PERMATRAN-W 3 It was measured under 37.8 degreeC, 100% RH (relative humidity) and 24 hours conditions with / 33 (made by MOCON).

Table 4

	Example
	One	2	3	4	5	6	7	8	9
Curing Shrinkage (%)	6.1	3.8	4.5	5.3	4.9	5.1	4.8	6.3	5.1
Storage modulus (MPa)	810	620	1140	790	760	880	810	850	910
Hardness (MPa)	72	63	94	71	68	72	68	71	77
Chlorine ion content (ppm)	0	0	0	0	0	0	0	0	0
Surface energy (mN / m)	33	30	42	34	31	37	36	32	35
Outgassing Amount (ppm)	101	125	132	108	107	113	128	123	185
Curing rate (%)	97.2	96.1	95.4	97.2	97.3	96.8	95.3	98.8	96.4
Transmittance (%)	96.1	96.2	95.8	95.1	95.6	95.4	95.2	95.5	95.3
Moisture permeability (g / m ² ㆍ day)	10 ^-6	10 ^-6	10 ^-7	10 ^-6	10 ^-6	10 ^-7	10 ^-7	10 ^-6	10 ^-7

Table 5

	Comparative example
	One	2	3	4	5	6	7	8
Curing Shrinkage (%)	16.1	14.2	15.3	14.1	15.7	14.5	21.3	23.4
Storage modulus (MPa)	3320	3640	2320	2510	2660	2830	4370	5150
Hardness (MPa)	305	321	249	261	258	295	383	437
Chlorine ion content (ppm)	72	77	48	51	48	51	122	131
Surface energy (mN / m)	28	30	25	26	40	41	25	27
Outgassing Amount (ppm)	97	96	138	136	142	134	95	92
Curing rate (%)	90.5	88.3	90.3	89.1	89.8	88.5	85.2	81.8
Transmittance (%)	95.1	95.2	95.3	95.7	95.2	95.4	95.2	95.5
Moisture permeability (g / m ² ㆍ day)	10 ^-5	10 ^-5	10 ^-5	10 ^-5	10 ^-7	10 ^-7	10 ^-5	10 ^-5

As shown in Table 4, the composition for encapsulation of the present invention has the effect of the above-mentioned curing shrinkage, modulus, hardness, surface energy, chlorine ion, curing rate, transmittance, moisture permeability after curing. As a result, the barrier stack on which the barrier layer is deposited can be used as the barrier stack of the display device. Accordingly, the present invention can form a barrier layer for encapsulation of an environmentally sensitive display device, can form a barrier layer with low permeability of oxygen and / or water vapor and / or moisture and / or chemicals, and an inorganic barrier. Provided is a composition for encapsulation and an encapsulated device including the same, which can implement a barrier layer having high adhesion to the layer and having a complementary effect with the inorganic barrier layer.

On the other hand, as shown in Table 5, the sealing composition of Comparative Example 7-8 containing only DDA and NDA did not implement one or more of the effects of the sealing composition of the present invention described above. In addition, the composition of Comparative Example 1-8, which does not include the monomer or oligomer of the present invention or contains 40% by weight or more of DDA and NDA, does not implement one or more of the effects of the encapsulation composition of the present invention. I couldn't.

The present invention is not limited to the above embodiments and drawings, but may be in various forms, and a person skilled in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that it may be implemented in a form. Therefore, it is to be understood that the embodiments and drawings described above are exemplary in all respects and not restrictive.

Claims

Comprising a photocurable mixture and an initiator,

The photocurable mixture comprises a di (meth) acrylate monomer of Formula 1 or an oligomer thereof in about 40 to 100% by weight of the photocurable mixture:

<Formula 1>

(In Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently of each other hydrogen, halogen, hydroxy group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted. An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms, At least one of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is a substituted or unsubstituted cycloalkyl group having 3-10 carbon atoms, a substituted or unsubstituted aryl group having 6-20 carbon atoms, or a substituted group Or an unsubstituted arylalkyl group having 7 to 21 carbon atoms,

Z 1 and Z 2 are each independently the following Chemical Formula 2a or Chemical Formula 2b.

<Formula 2a>

<Formula 2b>

(In Formulas 2a and 2b, * is a linking site,

R 30 is hydrogen or a methyl group,

Y is a substituted or unsubstituted C1-20 alkylene group, a substituted or unsubstituted C6-20 arylene group, a substituted or unsubstituted C7-21 arylalkylene group, or a substituted or unsubstituted C1 -20 alkyleneoxy groups,

n is an integer from 1 to 20).
The method of claim 1, wherein R 1 is a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R 2 , R 3 , R 4 , R 5 , And R 6 is a substituted or unsubstituted C 1-5 alkyl group.
The method of claim 1, wherein the photocurable compound further comprises at least one of a silicone (meth) acrylate monomer or an oligomer thereof represented by the following formula (3), a silicone (meth) acrylate monomer represented by the following formula (4) or an oligomer thereof Composition for encapsulation:

<Formula 3>

(In Formula 3, R 11 , R 12 , and R 13 are each independently hydrogen, halogen, hydroxy group, substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C3-10 cycloalkyl group, A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms, at least one of R 11 , R 12 , and R 13 is a substituted or unsubstituted C 3-10 cyclo; An alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms,

Z 1 is the following Chemical Formula 2a or Chemical Formula 2b.

<Formula 2a>

<Formula 2b>

(In Formulas 2a and 2b, * is a linking site,

R 30 is hydrogen or a methyl group,

Y is a substituted or unsubstituted C1-20 alkylene group, a substituted or unsubstituted C6-20 arylene group, a substituted or unsubstituted C7-21 arylalkylene group, or a substituted or unsubstituted C1 -20 alkyleneoxy groups,

n is an integer from 1 to 20),

<Formula 4>

(In Formula 4, R 21 , R 22 , and R 23 are independently of each other hydrogen, halogen, hydroxy group, substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C1-10 alkoxy group. At least one of R 21 , R 22 , and R 23 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms,

Z 1 is as defined above).
The compound of claim 3, wherein R 11 is a substituted or unsubstituted cycloalkyl group having 3-10 carbon atoms or a substituted or unsubstituted aryl group having 6-20 carbon atoms, and R 12 and R 13 are each independently substituted or unsubstituted. The composition for sealing which is a substituted C1-C5 alkyl group.
The photocurable mixture of claim 3, wherein the photocurable mixture comprises about 50-99.99% by weight of the di (meth) acrylate monomer or oligomer thereof and about 0.01-50% by weight of the silicone (meth) acrylate monomer or oligomer thereof of Formula 3 Composition for sealing containing.
The composition for encapsulation of claim 3, wherein R 21 , R 22, and R 23 are each independently a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms.
The photocurable mixture according to claim 3, wherein the photocurable mixture contains about 50-99.99% by weight of the di (meth) acrylate monomer or oligomer thereof and about 0.01-50% by weight of the silicone (meth) acrylate monomer of formula 4 or oligomer thereof. Composition for sealing containing.
The photocurable mixture of claim 3, wherein the photocurable mixture comprises about 40-80 wt% of the di (meth) acrylate monomer or oligomer thereof, about 10-50 wt% of the silicone (meth) acrylate monomer of formula 3 or oligomer thereof, And about 10-50% by weight of a silicone (meth) acrylate monomer or an oligomer thereof.
The composition for encapsulation of claim 1, wherein the di (meth) acrylate monomer is represented by the following Chemical Formula 1a:

<Formula 1a>

.
The composition for encapsulation of claim 3, wherein the monomer of Formula 3 is represented by Formula 3a, and the monomer of Formula 4 is represented by Formula 4a:

<Formula 3a>

<Formula 4a>

.
The composition for encapsulation of claim 1, wherein the initiator is included in an amount of more than 0 to about 2 parts by weight based on 100 parts by weight of the photocurable mixture.
The composition for encapsulation of claim 1 or 3, wherein the composition for encapsulation further comprises an antioxidant.
The composition for encapsulation of claim 12, wherein the composition for encapsulation comprises about 95-99% by weight of the photocurable mixture and about 1-5% by weight of the initiator and antioxidant.
Shrinkage after curing is about 10% or less,

The storage modulus after curing is about 200 MPa-2000 MPa,

Hardness after curing is about 50MPa-100MPa,

Chlorine ion content after curing is about 10 ppm or less,

After curing, the surface energy is at least about 30 mN / m,

The composition for sealing containing the di (meth) acrylate monomer of Claim 1, or its oligomer.
The method according to claim 14, wherein the photocurable compound is one of a silicone (meth) acrylate monomer or an oligomer thereof represented by the formula (3) of claim 3, one of the silicone (meth) acrylate monomer or an oligomer thereof represented by the formula (4) of claim 3 The composition for sealing further containing the above.
The composition for encapsulation of claim 15, wherein the composition further comprises an antioxidant.
Member for apparatus; and

A barrier stack formed over the device element, the barrier stack comprising an inorganic barrier layer and an organic barrier layer,

The encapsulated device, wherein the organic barrier layer is formed of the encapsulation composition of claim 1.
20. The method of claim 19, wherein the inorganic barrier layer is a metal, a nonmetal, an oxide thereof, a nitride thereof, a carbide thereof, an oxygen nitride thereof, an oxygen boronide thereof, or a mixture thereof, wherein the metal or nonmetal is silicon. (Si), selenium (Se), zinc (Zn), antimony (Sb), aluminum (Al), transition metal, lanthanide metal, indium (In), germanium (Ge), tin (Sn), bismuth (Bi) At least one of the encapsulated devices.
18. The method of claim 17, wherein the device member is a flexible organic light emitting device, an organic light emitting device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, An encapsulated device comprising an integrated circuit, a charge coupled device, a light emitting polymer, or a light emitting diode.