CN116999707A

CN116999707A - Optical instrument for phototherapy

Info

Publication number: CN116999707A
Application number: CN202210447804.0A
Authority: CN
Inventors: 庞惠卿; 保罗·E·伯罗斯; 谢梦兰
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2022-04-28
Filing date: 2022-04-28
Publication date: 2023-11-07

Abstract

Disclosed is an optical device for phototherapy, comprising a substrate and at least one photoluminescent layer; the photoluminescent layer comprises at least one photoluminescent material; the peak wavelength of the photoluminescence material absorption spectrum is in the wavelength range of ambient light, and the peak wavelength of the emission spectrum is above 660 nm; the photoluminescence layer is at least arranged on one side of the substrate; the light emitted by the photoluminescent layer is directed substantially towards the human skin. Such optical devices may be, but are not limited to, sunglasses, sunshades, hats, masks, and the like. Under the intense sun, when people wear the device, the photoluminescent material can be used for absorbing part of ambient light and emitting deep red and near infrared light, so that the device has a certain sun-proof effect, does not contain an additional light source, reduces energy consumption, and can also carry out phototherapy on skin. An optical article and a wearable optical article comprising the optical appliance are also disclosed. A method of making the optical device is also disclosed.

Description

Optical instrument for phototherapy

Technical Field

The present invention relates to an optical instrument for phototherapy. And more particularly to an optical device for phototherapy comprising a photoluminescent layer.

Background

In the middle and late 20 th century, techniques such as micro-light therapy (Low Light Laser Treatment) and photo bio-modulation (PBM) have been developed, and light is used as a means for treating diseases in the medical field (Michael r.hamulin, ying-Ying Huang, handbook of Photomedicine, CRC Press). In recent years, various researches show that the red light to near infrared light irradiation is beneficial to promoting regeneration of tissues such as collagen and skin cells, and can be applied to the fields of anti-wrinkle cosmetology, promotion of wound healing, freckle removal, scar removal and the like (Chan Hee Nam et al, dermatologic Surgery,2017,43:371-380;Daniel Barolet,Semin Cutan Med Surg,2008,27:227-238;Yongmin Jeon,Adv.Mater.Technol.2018,1700391). In vitro studies show that the visible light to near infrared band spectral region can trigger the synthesis of skin collagen. Furthermore, red light therapy is a useful tool to reduce redness and inflammation, especially to help reduce signs of aging. The specific red light wavelength can aim at the deep layer of the skin and promote the regeneration of tissues such as collagen and skin cells. The red light can not only reduce the inflammation of the surface layer of the skin, but also reduce deeper inflammation. Light of different wavelengths has different chromophores and has different effects on tissue. Wavelengths generally refer to the use of their associated colors, including blue, green, red, and near infrared light, and generally the longer the wavelength, the deeper the penetration of tissue. Fig. 1a shows the penetration depth of light of different wavelength bands into skin tissue (Daniel barlet, semin Cutan Med Surg,2008, 27:227-238), it can be seen that light with a wavelength of 600-1000nm can penetrate the dermis layer to a depth of 2-4mm below the skin. In determining the effective wavelength of the phototherapy light source, the absorption of the tissue must be taken into account in addition to the depth of penetration. At a wavelength of 600nm, blood hemoglobin (Hb) is the main obstacle to photon absorption, and further, at a wavelength of 1000nm, absorption of water starts to become strong. Fig. 1b shows the absorption of different wavelengths of light by different physiological substances (e.g. water, hemoglobin, oxyhemoglobin and melanin) (Daniel Barolet, semin Cutan Med Surg,2008, 27:227-238), it can be seen that the optimal wavelength band window capable of penetrating skin tissue without loss is approximately between 600-1400nm, which is the optimal choice for performing non-invasive phototherapy. In particular, the human eye is insensitive to the deep red light of 660nm or more and is not perceivable by the near infrared light of 750nm, so that if the light of 660nm or more is used for phototherapy on eyes and faces, normal vision is not affected.

Several studies showed that irradiance of 7.5mW/cm was used ² LED with wavelength of 640-680nm is used as light source, and daily dose is 5.17J/cm ² When the wrinkle removal effect is very remarkable (Chan Hee Nam et al Dermatologic Surgery,2017, 43:371-380). For various light with wavelength above 660nmIn the treatment, the irradiance is generally 8-50mW/cm ² In this case, the therapeutic effect is achieved (Daniel Barolet, semin Cutan Med Surg,2008, 27:227-238). On the other hand, it is generally believed that the total irradiance of the sun reaching the outside of the earth's atmosphere is 1360W/m ² (about 136 mW/cm) ² ) Of course, some loss will occur through the atmosphere, especially most of the short wavelength Ultraviolet (UV) light will be reflected back into space. Thus, the irradiance of the UV light in the 290-400nm band in the sunlight reaching the ground at normal midday is about 4.1mW/cm ² It can be seen from fig. 1c that this is only a small fraction of the total irradiation, whereas the main fraction of the total solar radiation is concentrated in a band above 400nm (nahan down et al International Journal of Research in Education and Science, volume 2,Issue 1,Winter 2016). If the irradiation of the wave band less than or equal to 700nm is taken into consideration, the sunlight irradiation reaching the ground can also be performed at 30-50mW/cm ² This is comparable to the irradiation dose required for phototherapy. The glass can block ultraviolet rays to a great extent, so that light waves which can be emitted into a room are mainly in a visible light wave band (400-700 nm), and general indoor illumination does not contain ultraviolet rays. Therefore, phototherapy can be performed if light energy of 700nm or less in ambient light can be converted into deep red or near infrared light of 660nm or more.

Applicant's prior patent application CN109956977a discloses various organic luminescent materials with Photoluminescence (PL) emission wavelengths of 681, 709 and 738nm, which can emit deep red and near infrared light with peak wavelengths above 660nm when excited by illumination. However, these applications disclose only compounds and only mention the doping of these compounds as light-emitting materials in host materials and the preparation of an organic electroluminescent device (OLED) with other organic functional layers, which suggests that there is a current through the light-emitting layer doped with organic light-emitting materials, but do not mention the use of these organic materials as a photoluminescent material.

Patent application US20200176625A1 mentions an optical component for greenhouse lighting, which functions to absorb light having a peak wavelength below 400nm and emit light having a wavelength between 400 and 1200nm by dispersing a series of fluorophores in a medium. The application proposes to provide such an optical component on the greenhouse glass of the cultivated plant, in order to increase the illuminance of the plant. The application of this application is to apply the optical member comprising the fluorophore to a greenhouse scene for the purpose of promoting photosynthesis of plants. Therefore, on one hand, the light emitted by the fluorophor acts on the plants, and on the other hand, the fluorophor mainly absorbs the light with short wavelength to convert the light into the visible light range which can be utilized by the plants, so that the effect of promoting the photosynthesis of the plants is better achieved. The application mainly absorbs the ambient light (as can be seen from fig. 2, the ambient light is mainly visible light with the wavelength of more than 400 nm), and emits the deep red light and the near infrared light with the wavelength of more than 660nm, thereby mainly acting on the skin of the human body to play a role in phototherapy.

US20090204186A1 discloses a retinal melatonin suppressor comprising a lens coated with a photoluminescent material, for example a quantum dot material, which is capable of emitting blue light towards the ball of the human eye under light excitation, thereby suppressing melatonin, and a filter material for attenuating the light emitted by the photoluminescent material. In order to achieve a better illumination effect, the application also proposes to provide photoluminescent material only in a partial region to obtain an optimal illumination angle. The photoluminescent material in this application must emit blue light (420-485 nm) to act on melatonin, which requires absorption of higher energy light, such as Ultraviolet (UV). The ultraviolet light in the absorbed ambient light is very weak, and is mainly excited by visible light of 400-700 nm, and deep red and near infrared light with peak wavelength of 660nm or more are emitted by using a photoluminescent material, so that the aim of phototherapy on human skin is achieved. Thus, the disclosed optical device differs substantially from this application, from excitation wavelength, to emission wavelength, to therapeutic purposes.

US20180024377A1 discloses an optical device with a marking function comprising an optical substrate on which is provided a photoluminescent material for use as a marking, and a layer of a colour-changing material which, when excited by actinic radiation, is capable of providing the photoluminescent material with a sufficiently long excitation time and causing it to glow, thereby exhibiting a marking pattern. The photoluminescent material in this application must be a pattern and occupy only a small area on the substrate, while the photoluminescent material in this application is excited by a color-changing material, not the ambient light in the present application; further, since the optical instrument of this application functions as a marker, the emitted light thereof needs to be visible light, whereas the instrument for phototherapy disclosed in the present application emits deep red and near infrared light which are insensitive or invisible to the human eye.

CN2838353Y discloses a luminous umbrella, which is provided with photoluminescent layers on the outer contour edge of the umbrella cover, the umbrella cap and the handle, has limited area, and mainly provides decorative effect for emitting visible light. The photoluminescent material absorbs ambient light to emit deep red and near infrared light with wavelengths above 660nm which are insensitive or invisible to the human eye, so as to perform sufficient and effective phototherapy towards the skin surface of the human body.

As can be seen from the above, the existing optical devices with photoluminescent layers on the market have limited light emitting layer arrangement area and are mainly used for marking and decoration, and no attention is paid to how to research and prepare an optical device with photoluminescent layers, so that people can fully utilize energy in ambient light when wearing or using the optical device, and achieve the effect of phototherapy on human body.

Disclosure of Invention

The present application aims to provide an optical device for phototherapy to solve at least some of the problems described above.

According to one embodiment of the present application, there is disclosed an optical instrument for phototherapy, comprising:

a substrate and at least one photoluminescent layer;

the photoluminescent layer comprises at least one photoluminescent material;

The peak wavelength of the photoluminescence material absorption spectrum is in the wavelength range of ambient light, and the peak wavelength of the emission spectrum is above 660 nm;

the photoluminescence layer is at least arranged on one side of the substrate;

the light emitted by the photoluminescent layer is directed substantially towards the human skin.

According to one embodiment of the invention, wherein the substrate is flexible.

According to one embodiment of the present invention, the material of the substrate is selected from one or more of the following: glass, plastic, semiconductor material, textile with pores.

According to one embodiment of the invention, wherein the substrate is part of an article of life.

According to one embodiment of the invention, wherein the living goods are selected from one or several of the following: lenses, umbrella covers, sun caps, masks, face masks, windshields, windows, ski goggles, sun-proof clothing, helmets.

According to one embodiment of the invention, wherein the photoluminescent material comprises one or several of the following: quantum dots, fluorescent powder, organic luminescent materials and perovskite materials.

According to one embodiment of the invention, the organic luminescent material is selected from small organic molecule materials.

According to one embodiment of the invention, wherein the absolute quantum yield (PLQY) of the photoluminescent material is 10% or more.

According to one embodiment of the invention, wherein the absolute quantum yield (PLQY) of the photoluminescent material is 20% or more.

According to one embodiment of the invention, wherein the absolute quantum yield (PLQY) of the photoluminescent material is 40% or more.

According to one embodiment of the invention, the organic small molecule material can be used as an OLED light emitting material.

According to one embodiment of the invention, the organic small molecule material is a phosphorescent light emitting material.

According to one embodiment of the invention, the peak wavelength of the photoluminescence material absorption spectrum is less than 700nm.

According to one embodiment of the invention, the peak wavelength of the photoluminescence material absorption spectrum is 600nm or less.

According to one embodiment of the invention, the peak wavelength of the photoluminescence material absorption spectrum is 550nm or less.

According to one embodiment of the invention, the peak wavelength of the photoluminescence material absorption spectrum is within the wavelength range of the solar spectrum.

According to an embodiment of the invention, the peak wavelength of the absorption spectrum of the photoluminescent material is in the band of 400-700nm in the solar spectrum.

According to one embodiment of the invention, wherein the peak wavelength of the photoluminescence material emission spectrum is between 680-2500 nm.

According to one embodiment of the invention, the photoluminescent material has an emission spectrum having a peak wavelength between 700 and 1400 nm.

According to one embodiment of the invention, the emitted light of the photoluminescent layer is directed substantially towards the head, face, periocular, neck and/or extremities of the human body.

According to one embodiment of the invention, the optical device does not comprise an additional light source.

According to one embodiment of the invention, the optical device does not comprise an electrode.

According to one embodiment of the invention, the optical device further comprises an encapsulation layer.

According to one embodiment of the invention, the encapsulation layer is a thin film encapsulation layer or cover glass.

According to one embodiment of the invention, the optical device further comprises an ultraviolet reflecting layer arranged on a side of the at least one photoluminescent layer close to the human body.

According to one embodiment of the invention, the optical device further comprises a near infrared reflecting layer arranged at a side of the at least one photoluminescent layer remote from the human body.

According to one embodiment of the invention, the substrate or encapsulation layer comprises the ultraviolet reflecting layer.

According to one embodiment of the invention, wherein the substrate or encapsulation layer comprises the near infrared reflecting layer.

According to one embodiment of the invention, wherein the photoluminescent layer has no current passing through it.

According to one embodiment of the invention, the optical device comprises a plurality of photoluminescent layers.

According to one embodiment of the invention, at least two of said photoluminescent layers are provided on both sides of said substrate.

According to one embodiment of the invention, an ultraviolet reflecting layer is arranged between at least two of said photoluminescent layers.

According to one embodiment of the invention, the area of the photoluminescent layer comprises more than 50% of the area of the substrate.

According to one embodiment of the invention, the area of the photoluminescent layer comprises more than 70% of the area of the substrate.

According to one embodiment of the invention, the area of the photoluminescent layer comprises more than 90% of the area of the substrate.

According to one embodiment of the present invention, an optical article is also disclosed, comprising the optical instrument of any one of the preceding embodiments.

According to one embodiment of the invention, wherein the optical article is a sunglass, a beach umbrella, a hat, a mask, a face shield, a windshield, a window, a ski goggles, a helmet or a sun protection garment.

According to one embodiment of the invention, there is also disclosed a wearable optical article comprising the optical device of any of the preceding embodiments.

According to an embodiment of the present invention, there is also disclosed a method for manufacturing the optical device according to any one of the preceding embodiments, including the steps of:

(1) Providing a substrate;

(2) The photoluminescent layer is disposed at least on one side of the substrate, the photoluminescent layer comprising at least one photoluminescent material.

Wherein the peak wavelength of the absorption spectrum of the photoluminescent material is in the wavelength range of ambient light, and the peak wavelength of the emission spectrum is above 660 nm.

According to an embodiment of the present invention, a method for manufacturing the optical device according to any one of the foregoing embodiments is disclosed, comprising the steps of:

(1) Providing a substrate; the material of the substrate is selected from one or more of the following materials: glass, plastic, semiconductor material, textile with pores.

(2) The photoluminescent layer is arranged at least on one side of the substrate, the area of the photoluminescent layer accounts for more than 50% of the area of the substrate, and the photoluminescent layer comprises at least one photoluminescent material.

According to an embodiment of the present application, a method for manufacturing the optical device according to any one of the foregoing embodiments is disclosed, comprising the steps of:

(1) Providing a substrate; the substrate is selected from a lens, umbrella cover, sun hat, mask, face shield, windshield, window, ski goggles, sun clothing or helmet.

The application discloses an optical appliance for phototherapy, which comprises a substrate, wherein at least one side of the substrate is plated with a photoluminescent layer, and can convert ambient light, preferably light with a wave band of 400-700nm into deep red and near infrared light with a wavelength of more than 660nm, and the area of at least 50% of the surface of the substrate is covered. The photoluminescent layer comprises at least one photoluminescent material including, but not limited to, phosphors, organic luminescent materials, quantum dot materials, perovskite materials, and the like. Such optical means may be, but are not limited to, sunglasses, sunshades, hats, masks, face masks, ski goggles, helmets, and the like. Under the intense sun, people wear the device, on one hand, the photoluminescent material can absorb part of ambient light, has a certain sun-proof effect, and can emit deep red and near infrared light to treat skin.

Drawings

Fig. 1a is a graph of penetration depth of light of different wavelengths into human skin.

FIG. 1b is a graph showing the absorption of different physiological substances (water, hemoglobin, oxyhemoglobin, melanin) for light in different wavelength bands.

FIG. 1c is a graph of irradiance of 240nm-1500nm light in the solar spectrum at different color temperatures.

Fig. 2a-2f are schematic structural views of an optical device.

FIG. 3a is a graph of the emission spectrum of Compound 1 at an excitation wavelength of 500 nm.

FIG. 3b is a graph of the emission spectrum of Compound 2 at an excitation wavelength of 500 nm.

Fig. 4a is a schematic diagram of the structure of glasses 400a with integrated optics.

Fig. 4b is a schematic view of the structure of a ski goggles 400b integrated with an optical device.

Fig. 4c is a schematic diagram of a mask 400c with integrated optics.

Fig. 4d is a schematic structural view of a helmet 400d with integrated optics.

Fig. 4e is a schematic structural view of a sunhat 400e with integrated optics.

Fig. 4f is a schematic structural view of a sunhat 400f with integrated optics.

Fig. 4g is a schematic view of the structure of a sunproof garment 400g incorporating optical means.

Fig. 5a is a schematic structural view of a hand-held parasol 500a with integrated optical devices.

Fig. 5b is a schematic view of the structure of the outdoor large sunshade 500b with the optical device integrated.

Fig. 5c is a schematic diagram of the structure of a window 500c incorporating an optical device.

Detailed Description

As used herein, "photoluminescent layer disposed at least on one side of the substrate" means that the photoluminescent layer may be "disposed" on one side of the substrate, or may be disposed on both sides of the substrate. The photoluminescent layer may or may not be in contact with the substrate (i.e., other layers may be present therebetween).

As used herein, "the emitted light of the photoluminescent layer is substantially directed toward the human skin" is intended to mean that the emitted light of the photoluminescent layer can cover at least a portion of the human skin (including, but not limited to, the human head, face, periocular, neck, and/or extremities) for phototherapy; preferably, more than 50% of the emitted light energy of the photoluminescent layer covers the skin of the human body; more preferably, 70% or more of the emitted light; most preferably, more than 90% of the light is emitted.

As used herein, "near infrared light" refers to light having wavelengths in the 700-2500nm band, and particularly, in the context of phototherapy applications, "near infrared light" may refer to a portion of the band, such as 700-1400 nm. As used herein, "Ultraviolet (UV) light" refers to light having a wavelength of less than 400 nm. As used herein, "visible light" refers to light having a wavelength between 400 and 700 nm. As used herein, "deep red light" refers to light having a wavelength of 660-700 nm.

As used herein, "above" a certain wavelength refers to a band of wavelengths greater than or equal to a certain wavelength, for example, "above 660 nm" refers to light having a wavelength of 660nm or more. Accordingly, at a certain wavelength "below" means a wavelength band smaller than (shorter than) or equal to the certain wavelength. For example, "400nm or less" means light having a wavelength of 400nm or less.

As used herein, "ambient light" refers to light emitted from the surrounding environment and "sunlight" refers to light in the universe that reaches the ground by solar radiation (also including light that reaches the ground by solar radiation reflected by the moon, such as moon light). If outdoors, the "ambient light" is typically sunlight; if in a room, "ambient light" generally includes sunlight that is emitted into the room, as well as light emitted by the room illumination. Because of the earth's surface atmosphere, most of the ultraviolet light and the wave bands below are reflected back to space when solar radiation in the universe reaches the ground, so that the outdoor "ambient light" is mainly visible light and part of near infrared light (the wavelength range is 400-1400 nm). Glass used in common buildings has an ultraviolet-proof effect, and indoor artificial lighting (such as incandescent lamps, fluorescent lamps, LEDs, OLEDs and the like) does not generally have ultraviolet bands, so that the ultraviolet bands in indoor 'ambient light' are very little.

As used herein, "small organic molecule material" refers to any organic or organometallic material that is not a polymer. The molecular weight of the small molecules can be large as long as they have a precise structure. Dendrimers with a well-defined structure can be considered as small molecules. Preferably, the small organic molecule refers to an organic compound having a molecular weight of 10000 or less; more preferably, an organic compound having a molecular weight of 5000 or less; most preferably, the molecular weight is below 2000.

As used herein, "quantum yield" refers to the utilization of light quanta in a photochemical reaction. Defined as the ratio of photons undergoing photochemical reactions to the total number of photons absorbed.

A graph of solar irradiance at sunny noon (color temperature 6000K) is shown in fig. 1c (Nathan down et al International Journal of Research in Education and Science, volume 2,Issue 1,Winter 2016), where the wavelength band from 400-700nm can be considered to be the visible band, below 400nm the ultraviolet and deep ultraviolet bands, and above 700nm the near infrared, infrared and microwave bands. In some areas with higher altitudes or adequate sunlight, solar irradiance is more intense. When people are in outdoor activities, these radiation will be directed completely to the bare skin without any protection or sun protection measures. Most sun-screening creams sold in the market at present adopt a mode of reflecting ultraviolet rays in sunlight to achieve the effect of protecting human skin from ultraviolet radiation. But viewed from another aspect the portion of the high energy uv light is fully available as an excitation light source that excites certain photoluminescent material to emit light of a particular wavelength. Indeed, other bands of light (including but not limited to blue, green, yellow, red, etc.) may be used as excitation light sources, not just ultraviolet light, but to photoluminescent materials that emit light of longer wavelengths. For example, an ultraviolet light with a peak wavelength of 400nm may excite the PbS quantum dots to emit light with a peak wavelength of 800nm, and a red light with a peak wavelength of 600nm may excite the PbS quantum dots to emit near infrared light with a peak wavelength of 1100 nm. (http:// www.mesolight.cc/products/yrxpbs. Html). A large number of medical researches prove that the radiation with the wave band of 600-1400nm is the optimal window for phototherapy, and can not only go deep into the skin of a human body, but also be not absorbed by various physiological substances. When people are exposed to sunlight, the sunlight can be fully utilized for phototherapy, and particularly, the irradiation of a large amount of visible light is converted into a wavelength band which is suitable for phototherapy. Since human eyes are very insensitive to light with the wave band above 660nm and almost indistinguishable from light with the wave band above 700nm, if ambient light, preferably light with the wave band shorter than 700nm in sunlight, is converted into light with the wave band between 660 and 1400nm and irradiates the skin surface of a human body, phototherapy can be carried out, normal vision cannot be affected, and the energy can be fully utilized.

Fig. 2a is a schematic diagram of an optical device 200 comprising a substrate 201, a photoluminescent layer 202, an encapsulation layer 203, a near infrared reflective layer 204 and an ultraviolet reflective layer 205, wherein the encapsulation layer 203, the reflective layers 204 and 205 are optional layers. The substrate 201 is a material having a high transmittance for near infrared light, and the transmittance is 50% or more, preferably 70% or more, and more preferably 90% or more. The substrate 201 is not necessarily a material having high transmittance in the visible light range, but preferably the substrate 201 also has high transmittance in the visible light range, such as glass, plastic, or textile with pores. The substrate may be part of other items including, but not limited to, lenses, umbrella covers, sun visors (including visors), masks, face masks, windshields, windows, ski goggles, sun visors, helmets (including helmet masks), and the like. A photoluminescent layer 202 is provided on the substrate 201 to achieve as large an irradiated area as possibleAnd phototherapy effects, the area of the photoluminescent layer 202 may occupy at least 50% or more, preferably 70% or more, more preferably 90% or more of the area of the substrate. The photoluminescent layer 202 comprises photoluminescent material that absorbs ambient light, preferably daylight, more preferably in the wavelength band of 400-700nm, and has an emission spectrum with a peak wavelength above 660nm, preferably between 700-2500nm, more preferably between 700-1400 nm. Among them, photoluminescent materials include, but are not limited to, phosphors, quantum dots, organic luminescent materials, perovskite materials, and the like. For example, patent applications EP2480626A2 and CN107573937A, CN109810709A, CN113845911A both mention the use of phosphors made of inorganic materials for down-converting light in the ultraviolet, blue and green bands into the near infrared band. Generally, quantum dots based on PbS (lead sulfide) can down-convert a short spectrum into near infrared to infrared, but Pb (lead) is a toxic substance and belongs to a strictly limited material in various countries such as the european union. US10517967B2 mentions a coated (encapsulated) SnS quantum dot material that can down-convert 690nm excitation light to 820-835nm near infrared light. Perovskite materials are a novel class of organic-inorganic composite materials, typically with ABX ₃ Is a specific crystal form of (a). Perovskite materials are also photoluminescent materials and can emit near infrared light upon excitation. For example, patent application CN114196404a discloses a double perovskite material that can emit light with a peak wavelength of 766nm under excitation with 464nm light. Finally, the small organic molecule material is also typically a photoluminescent material, preferably a luminescent material (emitter) in an organic electroluminescent device (OLED) because it typically has a very high absolute quantum efficiency. Especially, the phosphorescence luminescent material can regulate and control the emission wavelength and peak shape of the material by changing the position and the components of the groups, so as to emit light in deep red and near infrared bands. To increase the photo-conversion efficiency, the absolute quantum yield of the photoluminescent material should be above 10%, preferably above 20%, more preferably above 40%. The photoluminescent material in the photoluminescent layer 202, after absorbing light waves below 700nm, can be converted into deep red and near infrared light in the wavelength band above 660nm, preferably in the wavelength band 680-2500 nm, more preferably in the wavelength band 700-1400nm,and exits in the direction of the arrow in fig. 2 a. The light emitted by the photoluminescent layer 202 is directed to the skin of the human body and the light emitted therefrom covers the skin of various parts of the body including, but not limited to, the head, face, periocular, neck, and/or extremities of the human body. To protect the photoluminescent material from environmental (e.g., water, oxygen, etc.) or physical damage, an encapsulation layer 203 may be provided on the side of the photoluminescent layer 202 remote from the substrate. The encapsulation layer 203 may be a cover glass and is bonded to the substrate with a UV curable glue, but this approach adds bulk and weight and is not compatible with flexible substrates. Preferably, the encapsulation layer 203 is a flexible film, such as a plastic film, etc., more preferably, a semiconductor film or an organic film plated in a vacuum chamber, or a combination of the above forms, wherein the organic film may also be made using a solution method, such as Spin coating (Spin coating), screen Printing, ink Jet Printing (IJP), etc. In addition, a near infrared reflecting layer 204 may be disposed between the photoluminescent layer 202 and the encapsulation layer 203, so as to reflect near infrared light emitted from the photoluminescent layer 202 with a wavelength exceeding 660nm toward the substrate 201, i.e., toward the skin of the human body. In particular, for materials such as quantum dots, perovskite, etc., having a narrower emission spectrum, near infrared reflective layer 204 may be prepared to reflect only light at the peak wavelength of the emission spectrum of photoluminescent layer 202. Thus, the near infrared reflecting layer 204 can reflect most of the light emitted from the photoluminescent layer 202 toward the encapsulation layer 203 toward the human body surface (in the direction of the arrow), and can not reflect the near infrared light inherent in sunlight too much. Similarly, although the irradiance of the UV light in the 290-400nm wavelength band in sunlight is only a small fraction of the total irradiance, a similar manner can be used to provide an ultraviolet reflecting layer 205 between the substrate 201 and the photoluminescent layer 202 to reflect the ultraviolet light in sunlight for sufficient absorption and conversion by the electroluminescent layer 202, and to prevent the ultraviolet light that is not completely converted from leaking to the skin of the human body. The near infrared reflecting layer 204 and the ultraviolet reflecting layer 205 may both be optical films prepared by the bragg diffraction principle. The near infrared reflecting layer 204 may also be made of perovskite oxide material, as mentioned in patent US10144832B2 for example A component is not described in detail herein. The ultraviolet reflecting layer 205 may be formed by a coating layer containing titanium oxide (TiO 2) or silver particles. It is noted that the photoluminescent layer in the optical device of the present application does not pass current, which is essentially different from using photoluminescent layers for electroluminescent devices. At the same time, the optical device of the present application has no additional electroluminescent light source (e.g., OLED, LED, fluorescent lamp, incandescent lamp, etc.). The optical device utilizes the ambient light, especially the sunlight source, so that the optical device is more environment-friendly and sustainable, reduces the energy consumption and saves the energy. This is also a substantial distinction from many techniques in which a down-conversion layer is provided over an OLED or LED.

Fig. 2b is a schematic diagram of another optical device 210, in which a photoluminescent layer 212, an encapsulation layer 213, a near infrared reflecting layer 214, and an ultraviolet reflecting layer 215 are disposed under a substrate 211, and the outgoing light is still directed to the skin side of the human body (as indicated by arrows). In this case, the encapsulation layer 213 has a high transmittance for light having a wavelength of 660nm or more, and preferably has no transmittance for light having a wavelength of 400nm or less. Fig. 2c is a schematic structural diagram of another optical device 220, wherein the optical device 220 includes a substrate 221, a photoluminescent layer 222, an encapsulation layer 223, a near infrared reflective layer 224, and an ultraviolet reflective layer 225. Wherein the uv reflecting layer 225 is disposed under the substrate 221 by selecting a material stable in the environment. Finally, in the schematic structural diagram of another optical device 230 as shown in fig. 2d, only the substrate 231, the photoluminescent layer 232, and the encapsulation layer 233 are included, wherein the photoluminescent layer 232 is disposed between the substrate 231 and the encapsulation layer 233. At this time, the substrate 231 is selected to have a high transmittance of at least light in the 660nm or more wavelength band, and the transmittance is 50% or more, preferably 70% or more, more preferably 90% or more, and preferably the substrate 231 may include an ultraviolet reflective layer, that is, light having a wavelength of 400nm or less. The substrate 231 may be an optical film prepared by the bragg diffraction principle, including a semiconductor film layer. The encapsulation layer 233 may also include a near infrared reflecting layer. Of course, the physical positions of the encapsulation layer 233 and the substrate 231 may also be reversed, and are not shown. To increase the absorption of sunlight by the optical device, photoluminescent materials may also be provided on both sides of the substrate, as shown for the optical device 240 in fig. 2 e. The optical device 240 comprises a substrate 241, on both sides of which photoluminescent layers 2421 and 2422 are respectively provided, which may be chosen from the same materials, or may be different, preferably from the same materials. The encapsulation layers 2431 and 2432 are disposed on the sides of the photoluminescent layers 2421 and 2422 away from the substrate, respectively, to protect the photoluminescent layers from environmental water and oxygen and from direct human contact. Another optical device 250 is schematically illustrated in fig. 2f, which includes a first uv-reflective layer 2551 disposed on a substrate 251, a first photoluminescent layer 2521 disposed thereon, a second uv-reflective layer 2552 disposed thereon, a second photoluminescent layer 2522 disposed thereon, an encapsulation layer 253 disposed thereon, and an optional infrared reflective layer 254 disposed between the encapsulation layer and the second photoluminescent layer 2522. The structure of the optical device 250 as shown in fig. 2f can use multiple layers of thinner photoluminescent materials to improve the conversion efficiency and achieve better phototherapy effect. Of course, similarly, the optical device may also comprise 3 or more photoluminescent layers, which are not further shown here.

The following we list two specific examples of structurally different phosphorescent compounds that can be used as photoluminescent materials in the present invention:

we have chosen two structurally different phosphorescent materials (compound 1 and compound 2) that can be used as phosphorescent materials in OLEDs, and have measured their Photoluminescence (PL) spectra, respectively, as shown in figures 3a-3 b. The specific structures of compound 1 and compound 2 are shown below:

photoluminescence (PL) spectra of the above 2 compounds are shown in fig. 3a-3b, respectively. Low temperature Photoluminescence (PL) spectroscopic test method: the low-temperature photoluminescence spectrum of the relevant compound was measured using a fluorescence spectrophotometer model number prismatic light F98 manufactured by Shanghai prismatic light technologies, inc. Dissolving a sample to be tested in anhydrous 2-methyltetrahydrofuran to prepare the sample with the concentration of 10 ^- ⁵ The mol/L solution is filled into a low-temperature sample tube, then the low-temperature sample tube is put into a Dewar flask, liquid nitrogen is filled into the Dewar flask, and the liquid nitrogen amount is not more than 1/3 of the volume of the Dewar flask. Then the excitation wavelength is selected according to the properties of the corresponding compound to scan the sample to be detected, thus obtaining the low-temperature photoluminescence spectrum thereof, and the peak wavelength (lambda) can be directly read from the spectrum _max ) Corresponding data.

Specifically, the emission spectrum of Compound 1 at an excitation wavelength of 500nm is shown in FIG. 3a, the peak wavelength (lambda _max ) 668nm can be achieved, and the peak shape is wide, and contains more near infrared (more than 700 nm) light; the emission spectrum of Compound 2 at an excitation wavelength of 500nm is shown in FIG. 3b, the peak wavelength (lambda _max ) 687nm. Although the luminescent material with narrow peak width waveform as shown in fig. 3b has advantages in the organic electroluminescent device due to better color saturation and higher efficiency, the organic small molecular material with broad spectrum as shown in fig. 3a is rather popular in application to phototherapy, which is also quite different from the organic electroluminescent device made of the compounds directly. The organic micromolecular materials (OLED luminescent materials) emit deep red or near infrared light with the peak wavelength of more than 660nm under the excitation of light with the wavelength of more than 500nm, and the light in the wave bands can pass through the epidermis of the skin of a human body to reach the dermis, so that the phototherapy effect is realized.

As mentioned above, in addition to the requirements for deep red and near infrared luminescence, the absolute quantum yield of the photoluminescent material should be 10% or more, preferably 20% or more, more preferably 40% or more, in order to increase the light-induced conversion efficiency. Based on this, we measured the absolute quantum yields (PLQY) of compound 1 and compound 2 simultaneously.

PLQY test method: absolute quantum yield (PLQY) data of the related compounds were determined using an Absolute quantum yield tester model C11347-11 manufactured by Hamamatsu, japan. First, sample preparation: at a vacuum level of about 10 ^- ⁶ In the case of TorrIs used for steaming the samplePlating on a quartz substrate to prepare a film to be tested, wherein the 2 compounds are respectively doped into a main material compound H-1 at a doping concentration of 2%wt to form 2 film samples, and the total thickness of the samples is 200nm, so as to prevent compound quenching caused by excessive concentration. And secondly, PLQY test: the method comprises the steps of firstly scanning in a permissible wave band (250-850 nm) of an instrument by using a multi-wavelength excitation (Scan) mode, then selecting the optimal excitation wavelength, and measuring absolute quantum yield (PLQY) data by using a Single-wavelength excitation (Single) mode, wherein the operation in the test is completed in a glove box. The selection of the optimal excitation wavelength is based on: the excitation wavelength for PLQY testing of the compounds of the application was selected to be 300nm, which is the excitation wavelength that is capable of exciting the sample and corresponds to when PLQY is highest. The absolute quantum yields (PLQY) of compound 1 and compound 2, respectively, were 45% and 23% (see Table 1). It should be noted that the host material compound H-1 used in the test is only diluted to prevent the compound quenching phenomenon caused by the excessive concentration in the measurement, and the compound H-1 is not necessarily required in practical use.

The molecular structure of the host compound H-1 is as follows:

table 1 PLQY data for compound 1 and compound 2

Numbering of compounds	PLQY(％)
		Compound 1	45
Compound 2	23

As can be seen from the data in fig. 3a-3b and table 1, not only do the small organic molecular materials compound 1 and compound 2 emit at wavelengths that meet the requirements of phototherapy applications, they also have higher PLQY that represents higher conversion efficiency. For example, in the open noon on a sunny day, irradiance in the 400-700nm band in ambient light is 30mW/cm ² At this time, for compound 1, the irradiance of the down-converted outgoing light may reach 30×45% =13.5 mW/cm ² Irradiance of 7.5mW/cm was used compared to that used in the literature report (Chan Hee Nam et al Dermatologic Surgery,2017, 43:371-380) ² The energy of the LED light source with the peak wavelength of 640-680nm is almost doubled, so that more efficient phototherapy effect can be brought. For compound 2, irradiance of the down-converted emergent light can also reach 6.9mW/cm ² In addition to the irradiance of the ambient light itself above 660nm, it is also fully satisfactory for phototherapy applications. Meanwhile, phototherapy products with LEDs are generally used for 10-15 minutes each time to ensure 5.17J/cm ² Is a function of the energy of the (c). However, in the environment light, phototherapy can be performed while working and living because no additional appliance is needed, which is equivalent to the increase of the treatment time. So although irradiance was slightly below 7.5mW/cm for Compound 2 ² But can reach 5.17J/cm under the irradiation of ambient light for 12 minutes (compound 2) ² Is provided to achieve phototherapy effect. It should be noted that the above two compounds are only examples, and other organic small molecule materials satisfying the conditions can also be applied as photoluminescent materials in the optical device of the present invention.

Figures 4a-4g illustrate a series of wearable articles that can use the optical device described above with phototherapy effects. Fig. 4a is a schematic diagram of an eyeglass 400a comprising the optical device described above, and in particular, a lens portion thereof may comprise the optical device disclosed herein, the lens may be a substrate, and the photoluminescent layer may be coated on a side of the substrate (lens) facing the face or on a side facing away from the face (facing sunlight). Preferably, the glasses 400a are sunglasses. Similarly, figure 4b shows a schematic diagram of a ski goggles 400b using the optical device described above, again with photoluminescent layers applied to either side of the lens. The glasses 400a and the goggles 400b can convert partial wave bands (preferably 400nm-700nm wave bands) in sunlight into deep red and near infrared light to carry out phototherapy on the eye skin. At this time, the area of the photoluminescent layer occupies more than 50% of the total lens area, and preferably, the photoluminescent layer is disposed in the periocular region without covering the eyeball region, so as to prevent the outgoing light from directly directing to the eyeball. In addition to phototherapy of the eyes, the above-described optical device may be integrated into one mask 400c as shown in fig. 4c, so that phototherapy of facial skin can be performed. At this time, the substrate may be the mask itself, and the photoluminescent layer may be plated on the side of the mask away from the face (the side facing the external environment) to ensure that the photoluminescent layer does not directly contact the skin of the human body; the whole optical device can also be integrated on the mask, preferably on the side of the mask away from the face. Because most of the masks are made of non-woven fabrics, the middle part is provided with pores, and the masks are generally thinner, so that the transmission of infrared light is ensured. The area of the photoluminescent layer can occupy more than 50% of the whole mask area. Alternatively, the optical device described above may also be integrated on a helmet 400d as shown in fig. 4 d. The optical means described above may be integrated on the visor portion 401d of the helmet 400d or the visor may be directly used as a substrate, with a photoluminescent layer provided on either side thereof, preferably on the side facing the environment. At the moment, the photoluminescence layer of the mask part can convert partial wave bands in sunlight into deep red and near infrared light to carry out phototherapy on facial skin. The photoluminescent layer now occupies more than 50% of the total mask (excluding the head cover portion) area. The optical device may be integrated on the head cover portion 402d of the helmet 400d, or the head cover may be directly used as a substrate, and preferably, a photoluminescent layer is disposed on a side of the head cover away from the head (i.e., a side facing the environment) to avoid direct contact with human skin, so that a part of the wave band in the sunlight may be converted into deep red and near infrared light for hair growth treatment of the scalp. At this time, the material of the head cover should have high transmittance for deep red and near infrared light. The photoluminescent layer has an area that is at least 50% or more of the surface area of the hood (excluding the face piece portion). Of course, the mask portion 401d and the hood portion 402d may be provided with optical devices at the same time, and phototherapy may be performed on the face and the head. In addition, the optical device with phototherapy effect can be integrated on a hat, especially a sun hat, as shown in fig. 4e and 4 f. In the visor cap 400e shown in fig. 4e, the optical means may be integrated on the visor, or the visor itself may be a substrate, and the photoluminescent layer may be provided on either side of the visor. At this time, the photoluminescent layer can convert part of the wave band (preferably 400nm-700nm wave band) in the sunlight into deep red and near infrared light, at least part of the emitted light of the photoluminescent layer can cover the skin of the human face for phototherapy, and similarly, the material of the cap peak has higher transmittance to the deep red and the near infrared light. While in the sun helmet 400f shown in fig. 4f, the optical device may be provided on the visor 401f, on the roof 402f, or in both parts. The optical device also provided on the cap top 402f is preferably provided on the side away from the head to avoid direct contact with the skin of the human body, and the cap body is preferably made of a material having high transmittance for deep red and near infrared light. The photoluminescent layer comprises at least 50% of the area of the visor and/or the crown. Finally, the optical device can be integrated on clothes, such as a sun-proof clothes 400g shown in fig. 4g, and the photoluminescent layer occupies more than 50% of the whole sun-proof clothes surface area. The sun-proof garment 400g may be provided with an optical device on the side facing the environment, or the garment fabric may be directly used as a substrate, and a photoluminescent layer may be integrated thereon, and in this case, the garment fabric is preferably a material having high transmittance for deep red and near infrared light. When a user wears the sun-proof clothes 400g outdoors, the photoluminescence layer can convert partial wave bands in sunlight into deep red and near infrared light to carry out phototherapy on body skin, and meanwhile, the sun-proof clothes can play a role in sun-proof due to the fact that ultraviolet light is absorbed. Note that fig. 4g is only an illustration, and similar sun-protecting clothing may also be sun-protecting cuffs, scarves, etc.

The optical device with phototherapy effect described above may also be integrated in other non-wearing articles, as shown in fig. 5a-5 c. Fig. 5a and 5b are schematic structural views of a hand-held parasol 500a and an outdoor large parasol 500b, respectively, on which optical devices may be integrated on either side or a cover may be directly used as a substrate, on which a photoluminescent layer is provided. The umbrella surface material has higher transmittance to deep red and near infrared light. Therefore, under the sun, the sunshades 500a and 500b can not only shield strong sunlight, but also convert short-wavelength light in the sunlight into deep red and near infrared light to carry out phototherapy on human skin, and meanwhile, the sun protection effect is further improved due to the consumption of ultraviolet light. At this time, the area of the photoluminescent layer accounts for more than 50% of the area of the whole umbrella cover. In addition, such an optical device may be provided on the window, and a photoluminescent layer may be provided on the window 500c shown in fig. 5c, so as to convert a part of the wavelength band (preferably, the wavelength band of 400nm to 700 nm) in the sunlight outside the vehicle into deep red and near infrared light to phototherapy the skin surface of the human body. The photoluminescent layer occupies more than 50% of the total window area.

The optical device disclosed by the invention can convert the light with the wave band of 400-700nm in the environment light, preferably sunlight, into deep red and near infrared light with the wave band of more than 660nm, so as to carry out phototherapy on the skin of a human body. The optical device can be integrated on various articles, such as glasses, sunshades, hats and the like, and does not need to contain an additional light source in the optical device besides ensuring normal functions, so that the energy consumption is reduced, the additional phototherapy can be conveniently provided, a certain sun-proof effect is achieved, and multiple purposes are achieved.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. Thus, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. It is to be understood that the various theories as to why the present invention works are not intended to be limiting.

Claims

1. An optical device for phototherapy, comprising:

a substrate and at least one photoluminescent layer;

the photoluminescent layer comprises at least one photoluminescent material;

the photoluminescence layer is at least arranged on one side of the substrate;

2. The optical device of claim 1, wherein the substrate is flexible.

3. The optical device according to claim 1, wherein the material of the substrate comprises a material having a transmittance of 50% or more for light of 660nm or more; preferably, a material having a transmittance of 70% or more; more preferably, a material having a transmittance of 90% or more.

4. The optical device of claim 1, wherein the substrate is made of one or more of the following materials: glass, plastic, semiconductor material, textile with pores.

5. The optical appliance of claim 1 or 3, wherein the substrate is part of an article of life; preferably, the living goods are selected from one or more of the following: lenses, umbrella covers, sun caps, masks, face masks, windshields, windows, ski goggles, sun-proof clothing, helmets.

6. The optical appliance of claim 1, wherein the photoluminescent material comprises one or more of: quantum dots, fluorescent powder, organic luminescent materials and perovskite materials; preferably, wherein the organic luminescent material is selected from organic small molecule materials.

7. An optical device as claimed in claim 1 or 6, wherein the absolute quantum yield of the photoluminescent material is 10% or greater, preferably 20% or greater, more preferably 40% or greater.

8. The optical device according to claim 6, wherein the small organic molecule material is capable of being used as an OLED light emitting material, preferably the small organic molecule material is a phosphorescent light emitting material.

9. An optical device as claimed in claim 1, wherein the photoluminescence material absorption spectrum has a peak wavelength less than 700nm, preferably less than or equal to 600nm, more preferably less than or equal to 550nm.

10. The optical appliance of claim 1, wherein a peak wavelength of the photoluminescence material absorption spectrum is within a wavelength range of a solar spectrum; preferably, the peak wavelength of the absorption spectrum is in the band of 400-700nm in the solar spectrum.

11. An optical device as claimed in claim 1, wherein the photoluminescence material emission spectrum has a peak wavelength between 680-2500nm, preferably between 700-1400 nm.

12. The optical appliance of claim 1, wherein the photoluminescent layer emits light substantially toward the head, face, periocular, neck, and/or extremities of a human body.

13. The optical device of claim 1, wherein the optical device does not include an additional light source.

14. The optical device of claim 1, wherein the optical device further comprises an encapsulation layer.

15. The optical device of claim 14, wherein the encapsulation layer is a thin film encapsulation layer or a cover glass.

16. The optical device of claim 1 or 14, wherein the optical device further comprises an ultraviolet reflective layer disposed on a side of the at least one photoluminescent layer adjacent to the human body; preferably, the substrate or the encapsulation layer comprises the ultraviolet reflective layer.

17. The optical device of claim 1 or 14, wherein the optical device further comprises a near infrared reflective layer disposed on a side of the at least one photoluminescent layer remote from the human body; preferably, the substrate or the encapsulation layer comprises the near infrared reflecting layer.

18. The optical appliance of claim 1, wherein the photoluminescent layer has no current passing therethrough.

19. The optical device of claim 1, wherein the optical device comprises a plurality of photoluminescent layers.

20. An optical device as recited in claim 19, wherein at least two of the photoluminescent layers are disposed on both sides of the substrate.

21. The optical appliance of claim 19, wherein an ultraviolet reflective layer is disposed between at least two of the photoluminescent layers.

22. An optical device as claimed in claim 1, wherein the photoluminescent layer comprises more than 50%, preferably more than 70% of the area of the substrate; more preferably, 90% or more.

23. An optical article comprising the optical device of any one of claims 1-22; preferably, wherein the optical article is a sunglass, a beach umbrella, a hat, a mask, a face mask, a windshield, a window, a ski goggles, a helmet or sun clothing.

24. A wearable optical article comprising the optical appliance of any one of claims 1-22.

25. A method of making the optical device of any one of claims 1-22, comprising the steps of:

(1) Providing a substrate;

(2) Disposing the photoluminescent layer on at least one side of the substrate; the photoluminescent layer includes at least one photoluminescent material.