CN115132901A - Red light-near infrared light LED device and application thereof - Google Patents

Red light-near infrared light LED device and application thereof Download PDF

Info

Publication number
CN115132901A
CN115132901A CN202210647718.4A CN202210647718A CN115132901A CN 115132901 A CN115132901 A CN 115132901A CN 202210647718 A CN202210647718 A CN 202210647718A CN 115132901 A CN115132901 A CN 115132901A
Authority
CN
China
Prior art keywords
near infrared
red
led device
light
fluorescent powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210647718.4A
Other languages
Chinese (zh)
Inventor
陈雷
蒋婷
刘琦
吴亚兵
杨书淇
童国庆
蒋阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Intelligent Manufacturing Institute of Hefei University Technology
Original Assignee
Intelligent Manufacturing Institute of Hefei University Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Intelligent Manufacturing Institute of Hefei University Technology filed Critical Intelligent Manufacturing Institute of Hefei University Technology
Priority to CN202210647718.4A priority Critical patent/CN115132901A/en
Publication of CN115132901A publication Critical patent/CN115132901A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N5/0613Apparatus adapted for a specific treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N5/0613Apparatus adapted for a specific treatment
    • A61N5/0622Optical stimulation for exciting neural tissue
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/681Chalcogenides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials
    • H01L33/504Elements with two or more wavelength conversion materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N2005/065Light sources therefor
    • A61N2005/0651Diodes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N2005/0658Radiation therapy using light characterised by the wavelength of light used
    • A61N2005/0659Radiation therapy using light characterised by the wavelength of light used infrared
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N2005/0658Radiation therapy using light characterised by the wavelength of light used
    • A61N2005/0662Visible light
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/06Radiation therapy using light
    • A61N2005/0664Details
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008Processes
    • H01L2933/0033Processes relating to semiconductor body packages
    • H01L2933/0041Processes relating to semiconductor body packages relating to wavelength conversion elements

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Manufacturing & Machinery (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Pathology (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Inorganic Chemistry (AREA)
  • Radiology & Medical Imaging (AREA)
  • Neurosurgery (AREA)
  • Biophysics (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention belongs to the field of LED device preparation, and discloses a red light-near infrared light LED device and application thereof. The LED device is prepared by mixing red light-near infrared light fluorescent powder, transparent silica gel and optionally red light fluorescent powder and packaging by a packaging process; the chemical formula of the red light-near infrared light fluorescent powder is as follows: a (B) 1‑x Cr x ) 2 O 4 Wherein A is at least one of Mg, Ca and Sr, B is Ga and/or Sc, 0<x<0.10. The red light-near infrared light LED device can be used for treating gastrointestinal diseases and neurological diseases and supplementing other probioticsThe related diseases can also be used in other occasions needing red light and near infrared light.

Description

Red light-near infrared light LED device and application thereof
Technical Field
The invention belongs to the field of LED device preparation, and particularly relates to a red light-near infrared light LED device and application thereof.
Background
The high-quality development of semiconductor Light Emitting Diodes (LEDs) is an important development direction in the present stage. The development of the LED technology for plant illumination and ultraviolet sterilization is relatively mature at present, and for the LED technology for biomedical use, development is urgently needed, especially for the preparation of red-near infrared LED devices, for the following reasons: the red light-near infrared light single photon energy is low, the penetrability is strong, the absorption and excitation of a photoreceptor in an organism are satisfied, so the photon-near infrared light single photon energy can be used for treating diseases, particularly, medicines used for partial diseases cannot fundamentally treat and prevent the diseases, such as neurodegenerative diseases, and the problem needs to be fundamentally solved by developing a novel treatment means, wherein Photobiomodulation (PBM) has great potential in preventing and preventing the neuron degeneration, particularly:
parkinson's Disease (PD) and Alzheimer's Disease (AD) are two common neurodegenerative diseases of the elderly, seriously jeopardizing human life health and reducing quality of life. Typical symptoms of PD patients are unique motor deficits including tremor, rigidity, akinesia, and postural instability, often associated with the loss of dopaminergic cells of the substantia nigra pars compacta. Typical symptoms of AD patients are cognitive deficits, the main pathological features being synapses and neuronal degeneration as well as amyloid plaques and neurofibrillary tangles. In addition, mitochondrial dysfunction appears in PD and AD patients in the early stage or later stage of disease. At present, the medical community adopts drug treatment for treating two diseases, but the method only can relieve the symptoms of patients and cannot prevent or further prevent the neuron degeneration. Numerous studies have shown that PBM can promote neurons to release dopamine, a neurotransmitter capable of producing a large amount of ATP and increasing mitochondrial activity, and is considered as a final measure capable of fundamentally treating neurodegenerative diseases.
In addition to the typical pathological symptoms described above, another major symptom of PD and AD patients is intestinal dysfunction, often with symptoms of intestinal dysfunction in PD patients that are earlier than their typical motor deficit characteristics. The "brain-gut axis" mechanism is a widely accepted view of the pathogenesis of neurological diseases at present, i.e. the gut nervous system connects the gut to the central nervous system via nervous, hormonal and immunological signals, and the gut microbiome is an important signal source. Thus, one of the current ways to treat neurological disorders is to take probiotics and achieve positive therapeutic effects.
The influence of light on cellular energy metabolism is a commonly recognized action mechanism of PBM, and particularly, light acts on Cytochrome C Oxidase (CCO) in mitochondria to increase the permeability of the mitochondrial membrane, the active oxygen is transiently increased, a mitochondrial signal pathway related to neuroprotection and cell survival is activated, nitric oxide released by photodissociation of CCO and synthesis of CCO can stimulate vasodilation and blood flow, and ATP production is promoted by increasing oxygen consumption.
Light not only affects cellular metabolism, but also can modulate microbial activity. In addition to taking drugs that alleviate typical pathologies, an important strategy for PD, AD treatment is to modulate the patient's intestinal microbial profile according to the "brain-gut axis" mechanism, where lactic acid bacteria, as a typical probiotic, are of great significance for PD, AD treatment. Therefore, the PBM method is adopted to regulate the microorganisms in the brain-intestinal axis, is hopeful to complement the conventional medicine and surgical treatment, and has positive treatment effect on the neurological diseases.
Therefore, it is urgent to provide a new red-near infrared LED device to meet the requirement of non-invasive PBM treatment for neurological diseases.
Disclosure of Invention
The invention aims to provide a red light-near infrared light LED device and application thereof aiming at the defects of the prior art. The red light-near red light LED device can be used for treating gastrointestinal diseases, neurological diseases and other probiotic supplementing diseases.
In order to achieve the above object, a first aspect of the present invention provides a red-near infrared LED device, which is prepared by mixing red-near infrared phosphor, transparent silica gel, and optionally red phosphor, and encapsulating the mixture by an encapsulation process;
the chemical formula of the red light-near infrared light fluorescent powder is as follows: a (B) 1-x Cr x ) 2 O 4 Wherein A is at least one of Mg, Ca and Sr, B is Ga and/or Sc, 0<x<0.10。
According to the invention, preferably, the ratio of the dosage of the red light-near infrared light fluorescent powder to the dosage of the red light fluorescent powder to the dosage of the transparent silica gel is (1-3): (0-0.1): 1.
according to the present invention, the red phosphor has a chemical formula of (Ca, Sr) AlSiN 3 :Eu 2+ Or is M 2 Si 5 N 8 :Eu 2+ Wherein M is at least one of Sr, Ca, Ba and Mg.
According to the present invention, preferably, the packaging process includes: and (3) defoaming and degassing a mixture of the red light-near infrared light fluorescent powder, the transparent silica gel and the optional red light fluorescent powder, titrating the mixture on a blue light LED chip, and baking and curing to obtain the red light-near infrared light LED device.
According to the invention, the emission wavelength peak of the blue LED chip is preferably 400-500 nm.
According to the invention, preferably, the formula A (B) 1-x Cr x ) 2 O 4 Wherein x is selected from the following values: 0.0025<x<0.03, and more preferably, x is 0.01.
According to the present invention, preferably, the preparation method of the red-near infrared phosphor comprises the following steps: the first step is as follows: will contain Cr 3+ The raw material of (2) and the raw material containing the element B are ground and mixed uniformly, and are calcined for the first time to obtain a first-step product;
the second step is that: grinding and uniformly mixing the raw material containing the element A, the first-step product and the fluxing agent, and carrying out second calcination to obtain a second-step product;
the third step: and grinding the product obtained in the second step, calcining for the third time, crushing, grinding, washing, filtering and drying to obtain the red light-near infrared light fluorescent powder.
According to the invention, it is preferred that in a first step Cr is first present 3+ Incorporating the raw material containing the B element, sufficiently grinding the raw material containing the B element and the raw material containing Cr in air or N 2 The first step of calcination is carried out under the operating conditions comprising: heating to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 0.8-1.2 hours, heating to 1400-1500 ℃ at 3-8 ℃/min, keeping the temperature for 1-5 hours, cooling to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 0.5-2 hours, cooling to 250-350 ℃ at 3-10 ℃/min, cutting off the power, and cooling to room temperature (25-30 ℃) along with the furnace.
According to the present invention, preferably, in the second step, the raw material containing the a element and the flux are added to the product of the first step, and then sufficiently ground and uniformly mixed, and then dehydrated and degassed by low-temperature calcination (second calcination) under the operating conditions of: heating to 300 ℃ at a rate of 3-10 ℃/min, keeping the temperature for 0.5-2 hours, heating to 1000 ℃ at a rate of 3-10 ℃/min, keeping the temperature for 0.5-3 hours, cooling to 350 ℃ at a rate of 250 ℃ at a rate of 3-10 ℃/min, cutting off the power, and cooling to room temperature (25-30 ℃) along with the furnace.
According to the present invention, preferably, in the third step, the second step product is fully ground and then subjected to a third calcination, wherein the third calcination is performed under the following operating conditions: heating to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 1 hour, heating to 1100-1500 ℃ at 3-8 ℃/min, keeping the temperature for 2-12 hours, cooling to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 0.5-2 hours, cooling to 250-350 ℃ at 3-10 ℃/min, cutting off the power, and cooling to room temperature (25-30 ℃) along with the furnace.
According to the present invention, it is preferable that the raw material containing the element B is at least one of an oxide, a nitrate, an oxalate, and a carbonate containing the element B.
According to the present invention, preferably, the raw material containing the element a is at least one of an oxide, a nitrate, an oxalate, and a carbonate containing the element a.
According to the invention, the addition amount of the fluxing agent is preferably 1-2.5% of the total mass of the raw materials used for preparing the red-near infrared fluorescent powder.
According to the present invention, preferably, the flux is at least one of aluminum fluoride, barium fluoride, ammonium chloride, ammonium fluoride, ammonium bifluoride, and boric acid, and preferably, the flux is boric acid.
According to the invention, preferably, the emission wavelength range of the red-near infrared light LED device is 600-1050nm, and the emission wavelength peak value is 700-730 nm.
The invention provides application of the red light-near infrared light LED device as a light source for treating gastrointestinal diseases, neurological diseases and juvenile myopia. In the invention, the red light-near infrared light LED device is used as a light source manufactured by using the device and medical instruments and equipment manufactured by using the device and a light-emitting device. The application of the invention, including but not limited to medical instruments and equipment, can also be other applications developed by using the near-infrared LED device manufactured by the invention.
The technical scheme of the invention has the following beneficial effects:
(1) compared with a laser light source, the light source generated by the red light-near infrared light LED device has the remarkable advantages of low cost, portability and the like, particularly, the emission spectrum of the light source is a wide band spectrum and is consistent with the wide band absorption of a light receptor in an organism, and compared with the linear light of the laser light source, the light source is more suitable for PBM.
(2) The research of using the red light-near infrared light LED device to carry out light irradiation on the lactobacillus to adjust the activity shows positive influence, and further proves the important reference value of the device for adjusting the brain-intestine axis of the nervous diseases.
(3) The red light-near infrared light LED device can be used for medical light sources and equipment, treating gastrointestinal diseases, nervous diseases (stimulating secretion and growth of dopamine and neurons, having important significance for prevention, control and treatment of the nervous diseases and complications such as Parkinson's disease and Alzheimer's disease) and other probiotic supplementation related diseases, and can also be used for other purposes.
(4) Under the drive current of 100mA, the light output power of the red light-near infrared light LED device is 53.71mW, and the photoelectric conversion efficiency is 18.08%. The maximum light output power under the drive current of 20-320mA is 111.9mW, the maximum photoelectric conversion efficiency is 27.12 percent, and the industrialization level is reached.
(5) The red light-near infrared light fluorescent material used by the invention has a spinel or spinel-like crystal structure, the emission wavelength range of the preferred fluorescent material is 600-1050nm, and the emission wavelength peak value is 700-730 nm; two excitation bands are arranged at 350-700nm, so that the blue light can be effectively excited; the absorptivity and internal and external quantum efficiency of the red light-near infrared light fluorescent material are respectively 35.4%, 81.1% and 28.7%.
(6) The light source emitted by the red light-near infrared light fluorescent material can promote the growth of intestinal lactobacillus of an organism, promote the expression of anti-inflammatory factors and promote the balance of intestinal flora in the organism by regulating the activity of cells in the organism, and has prevention, control and treatment effects on preventing and treating nervous diseases such as Parkinson's disease and Alzheimer's disease.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings, wherein like reference numerals generally represent like parts in the exemplary embodiments of the present invention.
FIG. 1 shows the emission spectra of red-near infrared phosphors provided in examples 1-5 of the present invention.
FIG. 2 shows the excitation spectra of red-NIR phosphors provided in examples 1-5 of the present invention.
FIG. 3 shows a compound represented by Mg (Ga) provided by the present invention 0.99 Cr 0.01 ) 2 O 4 And the red light-near infrared light LED device obtained by packaging the fluorescent powder has a light emission spectrum under different driving currents.
FIG. 4 shows a compound represented by Mg (Ga) provided by the present invention 0.99 Cr 0.01 ) 2 O 4 The red light-near infrared light LED device obtained by packaging the fluorescent powder has the photoelectric conversion efficiency and the light output power curve which change along with the current.
FIG. 5 shows emission spectra of red-near infrared phosphors provided by comparative examples 1 to 5 of the present invention.
FIG. 6 shows the excitation spectra of the red-near infrared phosphors provided in comparative examples 1 to 5 of the present invention.
FIG. 7 is a graph showing the comparison of the integrated areas of the emission spectra of the red-near infrared phosphors provided in examples 1 to 5 of the present invention and comparative examples 1 to 5.
FIG. 8 shows emission spectra of red-near infrared phosphors provided in comparative examples 6 to 7 of the present invention.
FIG. 9 shows excitation spectra of red-near infrared phosphors provided by comparative examples 6 to 7 of the present invention. FIG. 10 shows emission spectra of red-near infrared phosphors provided by comparative examples 8 to 12 of the present invention.
FIG. 11 shows the excitation spectra of the red-NIR phosphors provided in comparative examples 8-12 of the present invention.
FIG. 12 shows emission spectra of red-near infrared phosphors provided in comparative examples 13 to 16 of the present invention.
FIG. 13 shows excitation spectra of red-NIR phosphors provided in comparative examples 13-16 of the present invention.
FIG. 14 shows emission spectra of red-near infrared phosphors provided by comparative examples 17 to 20 of the present invention.
FIG. 15 shows excitation spectra of red-NIR phosphors provided by comparative examples 17-20 of the present invention.
FIGS. 16(a) - (b) show the growth of lactic acid bacteria after 24h incubation (no light (a) and 720nm light (b)) in the test examples of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the following examples, the raw materials used to prepare the red-near infrared phosphor include: MgO (98.5%), CaCO 3 (99%)、SrCO 3 (99%)、Sc 2 O 3 (99.99%)、Ga 2 O 3 (99.99%) and Cr 2 O 3 (99.99%)。
Examples 1-5, the red-near infrared phosphor has the formula: mg (Ga) 1-x Cr x ) 2 O 4 And x is 0.0025, 0.005, 0.01, 0.02 and 0.03 respectively.
Example 1, x is 0.01
The embodiment provides a red light-near infrared light LED device, which is prepared by defoaming and degassing a mixture of red light-near infrared light fluorescent powder, red light fluorescent powder and transparent silica gel, titrating the mixture on a blue light LED chip with an emission wavelength peak value of 450nm, and baking and curing the blue light LED chip;
the ratio of the dosage of the red light-near infrared light fluorescent powder, the dosage of the red light fluorescent powder and the dosage of the transparent silica gel is 1.8: 0.01: 1.
the chemical formula of the red light phosphor powder is (Ca, Sr) AlSiN 3 :Eu 2+
The chemical formula of the red light-near infrared light fluorescent powder is as follows: mg (Ga) 0.99 Cr 0.01 ) 2 O 4 The emission spectrum and excitation spectrum are shown in fig. 1 and 2.
The red light-near infrared light fluorescent powder comprises the following synthesis steps:
first, Cr is first added 3+ By doping a raw material containing a B element, the raw material containing the B element (Ga) is sufficiently ground 2 O 3 ) And a raw material containing Cr (Cr) 2 O 3 ) And carrying out the first calcination step in air under the operating conditions including: heating to 900 deg.C at 4 deg.C/min, holding for 1 hr, heating to 1400 deg.C at 4 deg.C/min, holding for 2 hr, cooling to 900 deg.C at 4 deg.C/min, holding for 1 hr, cooling to 350 deg.C at 4 deg.C/min, cutting off power, and cooling to room temperature.
In the second step, a raw material (MgO) containing an element A and a flux (H) are added to the product of the first step 3 BO 3 ) Then fully grinding, uniformly mixing, and then carrying out dehydration and degassing treatment by low-temperature calcination (second calcination), wherein the operation conditions of the second calcination comprise: heating to 176 deg.C at 4 deg.C/min, holding for 2 hr, heating to 900 deg.C at 4 deg.C/min, holding for 2 hr, cooling to 350 deg.C at 4 deg.C/min, cutting off power, and cooling to room temperature.
And step three, fully grinding the product obtained in the step two, and then calcining for the third time, wherein the operating conditions of the calcination for the third time comprise: heating to 900 ℃ at a speed of 4 ℃/min, preserving heat for 1 hour, heating to 1300 ℃ at a speed of 4 ℃/min, preserving heat for 7 hours, cooling to 900 ℃ at a speed of 4 ℃/min, preserving heat for 1 hour, cooling to 350 ℃ at a speed of 4 ℃/min, cutting off power, cooling to room temperature along with the furnace, crushing, grinding, washing, filtering and drying to obtain the red light-near infrared light fluorescent powder.
When Cr is contained in examples 1 to 5 and shown in FIGS. 1 and 2 3+ When the concentration x is 0.01, the emission peak is the strongest at 717 nm. Emission wavelength and spectrum configuration with Cr 3+ The significant variation in concentration is due to the different concentrations of Cr 3+ Different lattice positions may be occupied when entering the crystal lattice, the crystal field intensity is changed, and Cr in the fluorescent powder is subjected to 3+ Is/are as follows 4 T 2g (F)→ 4 A 2g (F) The transition has a greater effect, and 2 E g (G)→ 4 A 2g (F) the spin-forbidden transition of (a) is less affected by the variation of the crystal field strength.
Cr 3+ At a concentration of x equal to 0.01, with Mg (Ga) 0.99 Cr 0.01 ) 2 O 4 The red light-near infrared light LED device packaged by the fluorescent powder achieves the strongest emission at 718nm under the drive current of 100mA, the light output power of the device is 53.71mW, the photoelectric conversion efficiency is 18.08%, and in addition, the maximum light output power of the device under the drive current of 20-320mA is 111.9mW, and the maximum photoelectric conversion efficiency is 27.12%, as shown in figures 3 and 4.
Comparative examples 1 to 5, the red-near infrared phosphorThe chemical formula of (A) is: mg (Ga) 1-x Cr x ) 2 O 4 X is 0.0025, 0.005, 0.01, 0.02 and 0.03 respectively, and the preparation method adopts a two-step synthesis method.
Comparative example 1, x is 0.01
The comparative example differs from example 1 only in the synthesis method, which is a two-step synthesis method, and the specific synthesis steps are as follows:
first, raw materials (MgO, Ga) containing element A and element B are sufficiently ground 2 O 3 ) And a raw material containing Cr (Cr) 2 O 3 ) Adding flux (H) 3 BO 3 ) And a first calcination step carried out in air, the operating conditions comprising: heating to 176 deg.C at 4 deg.C/min, holding for 2 hr, heating to 900 deg.C at 4 deg.C/min, holding for 2 hr, cooling to 350 deg.C at 4 deg.C/min, cutting off power, and cooling to room temperature (25-30 deg.C).
And step two, fully grinding the product, and then performing secondary calcination, wherein the operation conditions of the secondary calcination comprise: heating to 900 ℃ at a speed of 4 ℃/min, preserving heat for 1 hour, heating to 1300 ℃ at a speed of 4 ℃/min, preserving heat for 7 hours, cooling to 900 ℃ at a speed of 4 ℃/min, preserving heat for 1 hour, cooling to 350 ℃ at a speed of 4 ℃/min, cutting off power, cooling to room temperature (25-30 ℃) along with a furnace, crushing, grinding, washing, filtering and drying to obtain the red light-near infrared light fluorescent powder.
FIGS. 5 and 6 show the fluorescent powder Mg (Ga) prepared by the two-step synthesis method 1-x Cr x ) 2 O 4 And (x is 0.0025, 0.005, 0.01, 0.02 and 0.03), comparing the emission and excitation spectrograms of the same fluorescent powder obtained by the three-step synthesis method, performing area integration on the luminous intensity of the fluorescent powder obtained under two synthesis conditions, and obtaining an integration result as shown in fig. 7.
Comparative example 6
The present comparative example provides a red-near infrared LED device, and differs from comparative example 1 only in that: the chemical formula of the red light-near infrared light fluorescent powder is as follows: ca (Sc) 0.99 Cr 0.01 ) 2 O 4 Adopts a two-step synthesis method, and the calcination environment is N 2 The resulting mixture was incubated at 1500 ℃ for 6 hours without adding flux, and the emission spectrum and excitation spectrum thereof are shown in FIGS. 8 and 9.
The specific synthesis steps are as follows:
in the first step, a raw material (CaCO) containing an element A and an element B is sufficiently ground 3 、Sc 2 O 3 ) And a raw material containing Cr (Cr) 2 O 3 ) And carrying out a first step of calcination under the operating conditions comprising: n is a radical of 2 Heating to 176 deg.C at 4 deg.C/min, holding for 2 hr, heating to 900 deg.C at 4 deg.C/min, holding for 2 hr, cooling to 350 deg.C at 4 deg.C/min, cutting off power, and cooling to room temperature (25-30 deg.C).
And step two, fully grinding the product, and then performing secondary calcination, wherein the operation conditions of the secondary calcination comprise: n is a radical of 2 Heating to 900 ℃ at a speed of 4 ℃/min in the environment, preserving heat for 1 hour, heating to 1500 ℃ at a speed of 4 ℃/min, preserving heat for 6 hours, cooling to 900 ℃ at a speed of 4 ℃/min, preserving heat for 1 hour, cooling to 350 ℃ at a speed of 4 ℃/min, powering off, cooling to room temperature (25-30 ℃) along with a furnace, crushing, grinding, washing, filtering and drying to obtain the red-light near-infrared fluorescent powder.
Comparative example 7
The present comparative example provides a red-near infrared LED device, and differs from comparative example 6 only in that: the chemical formula of the red light-near infrared light fluorescent powder is as follows: sr (Sc) 0.99 Cr 0.01 ) 2 O 4 The emission spectrum and excitation spectrum are shown in fig. 8 and 9.
The procedure for synthesizing the phosphor in this comparative example was the same as in comparative example 6.
Comparative examples 8 to 12
Comparative examples 8 to 12 provide Mg (Ga) 0.99 Cr 0.01 ) 2 O 4 The preparation method of the fluorescent powder, and the comparative examples 8 to 12 are different from the comparative example 1 only in that: the two-step synthesis method is adopted, the temperature of the second time in the second calcination is respectively raised to 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃, the heat preservation time is 6h, and no fluxing agent is added.
The emission spectra and excitation spectra of the red-near infrared phosphors of comparative examples 8 to 12 are shown in FIGS. 10 and 11.
Comparative examples 13 to 16
Comparative examples 13 to 16 provide Mg (Ga) 0.99 Cr 0.01 ) 2 O 4 The preparation method of the fluorescent powder, and the comparative examples 13 to 16 are different from the comparative example 1 only in that: the two-step synthesis method is adopted, the holding time after the second temperature rise to 1300 ℃ in the second calcination is respectively 4, 5, 7 and 8 hours, and no fluxing agent is added.
The emission spectra and excitation spectra of the red-near infrared phosphors of comparative examples 13 to 16 are shown in FIGS. 12 and 13.
Comparative examples 17 to 20
Comparative examples 17 to 20 provide Mg (Ga) 0.99 Cr 0.01 ) 2 O 4 The preparation method of the fluorescent powder, and the comparative examples 17 to 20 are different from the comparative example 1 only in that: a two-step synthesis method is adopted, in the second calcination process, the temperature is kept at 1300 ℃ for 7 hours, different types of fluxing agents are added, namely aluminum fluoride, barium fluoride and ammonium fluoride, and no fluxing agent is used.
The emission spectra and excitation spectra of the red-near infrared phosphors of comparative examples 17 to 20 are shown in FIGS. 14 and 15.
Test example
This test example utilized a red-near infrared LED device Mg (Ga) 0.98 Cr 0.02 ) 2 O 4 Performing light-induced lactobacillus experiment, culturing lactobacillus in 37 deg.C constant temperature incubator in dark place for 24 hr by solid culture method, wherein the concentration of lactobacillus in the solid culture medium is controlled within a range of 30-300cfu/ml, and the lactobacillus in the culture medium receives 20mW/cm per day 2 Light dose, irradiation density 1.5J/cm 2 Irradiating by pulse for 3 times a day, each time irradiation is 0.5J/cm 2 Colonies in each medium were counted or aligned 2h after the end of the last illumination. FIGS. 16(a) - (b) are the culture medium after 24h culture, (a) is dark culture without light, and (b) is Mg (Ga) using red-near infrared LED device 0.98 Cr 0.02 ) 2 O 4 To proceed withThe culture medium of PBM can obviously see that the lactobacillus irradiated by 720nm grows in a sheet connection mode, and cannot be counted because the lactobacillus grows too fast and densely, but macroscopically proves that the light source can promote the growth of the lactobacillus. The red light-near infrared light LED device Mg (Ga) combines the action mechanism of lactic acid bacteria in PD and AD 0.98 Cr 0.02 ) 2 O 4 And the emitted light can promote the growth of probiotics represented by lactic acid bacteria, so that the treatment of the neurological diseases is realized.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A red light-near infrared light LED device is characterized in that the LED device is prepared by mixing red light-near infrared light fluorescent powder, transparent silica gel and optional red light fluorescent powder and packaging the mixture by a packaging process;
the chemical formula of the red light-near infrared light fluorescent powder is as follows: a (B) 1-x Cr x ) 2 O 4 Wherein A is at least one of Mg, Ca and Sr, B is Ga and/or Sc, 0<x<0.10。
2. The red-near infrared LED device according to claim 1, wherein the ratio of the amount of the red-near infrared phosphor to the amount of the red phosphor to the amount of the transparent silica gel is (1-3): (0-0.1): 1;
the chemical formula of the red phosphor is (Ca, Sr) AlSiN 3 :Eu 2+ Or is M 2 Si 5 N 8 :Eu 2+ Wherein M is at least one of Sr, Ca, Ba and Mg.
3. The red-near infrared LED device of claim 1, wherein the packaging process comprises: and (3) defoaming and degassing a mixture of the red light-near infrared light fluorescent powder, the transparent silica gel and the optional red light fluorescent powder, titrating the mixture on a blue light LED chip, and baking and curing to obtain the red light-near infrared light LED device.
4. The red-near infrared LED device of claim 3, wherein the peak emission wavelength of the blue LED chip is 400-500 nm.
5. The red-near infrared LED device of claim 1, wherein the formula a (B) 1-x Cr x ) 2 O 4 Wherein x is selected from the following values: 0.0025<x<0.03。
6. The red-near infrared LED device according to claim 1 or 5, wherein the method for preparing the red-near infrared phosphor comprises the steps of:
the first step is as follows: will contain Cr 3+ The raw material of (2) and the raw material containing the element B are ground and mixed uniformly, and are calcined for the first time to obtain a first-step product;
the second step is that: grinding and uniformly mixing the raw material containing the element A, the first-step product and the fluxing agent, and carrying out second calcination to obtain a second-step product;
the third step: and grinding the product obtained in the second step, calcining for the third time, crushing, grinding, washing, filtering and drying to obtain the red light-near infrared light fluorescent powder.
7. The red-near infrared LED device of claim 6, wherein the operating conditions of the first calcination comprise: in the air or N 2 Heating to 850-950 ℃ at a speed of 3-10 ℃/min, preserving heat for 0.8-1.2 hours, heating to 1400-1500 ℃ at a speed of 3-8 ℃/min, preserving heat for 1-5 hours, cooling to 850-950 ℃ at a speed of 3-10 ℃/min, preserving heat for 0.5-2 hours, cooling to 250-350 ℃ at a speed of 3-10 ℃/min, powering off, and cooling to 25-30 ℃ along with the furnace;
the operating conditions of the second calcination include: in the air or N 2 In the middle ofHeating to 100-300 ℃ at a rate of 3-10 ℃/min, preserving heat for 0.5-2 hours, heating to 500-1000 ℃ at a rate of 3-10 ℃/min, preserving heat for 0.5-3 hours, cooling to 250-350 ℃ at a rate of 3-10 ℃/min, cutting off power, and cooling to 25-30 ℃ along with the furnace;
the operating conditions of the third calcination include: in the air or N 2 Heating to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 1 hour, heating to 1100-1500 ℃ at 3-8 ℃/min, keeping the temperature for 2-12 hours, cooling to 850-950 ℃ at 3-10 ℃/min, keeping the temperature for 0.5-2 hours, cooling to 250-350 ℃ at 3-10 ℃/min, cutting off the power, and cooling to 25-30 ℃ with the furnace.
8. The red-near infrared LED device of claim 6,
the raw material containing the element B is at least one of oxide, nitrate, oxalate and carbonate containing the element B;
the raw material containing the element A is at least one of oxide, nitrate, oxalate and carbonate containing the element A;
the addition amount of the fluxing agent is 1-2.5% of the total mass of the raw materials used for preparing the red light-near infrared light fluorescent powder;
the fluxing agent is at least one of aluminum fluoride, barium fluoride, ammonium chloride, ammonium fluoride, ammonium bifluoride and boric acid, and preferably the fluxing agent is boric acid.
9. The red-nir LED device according to any one of claims 1-8, wherein the emission wavelength range of the red-nir LED device is 600-1050nm and the emission wavelength peak is 700-730 nm.
10. Use of a red-near infrared LED device according to any one of claims 1-9 as a light source for the treatment of gastrointestinal, neurological and juvenile myopia.
CN202210647718.4A 2022-06-09 2022-06-09 Red light-near infrared light LED device and application thereof Pending CN115132901A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210647718.4A CN115132901A (en) 2022-06-09 2022-06-09 Red light-near infrared light LED device and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210647718.4A CN115132901A (en) 2022-06-09 2022-06-09 Red light-near infrared light LED device and application thereof

Publications (1)

Publication Number Publication Date
CN115132901A true CN115132901A (en) 2022-09-30

Family

ID=83377654

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210647718.4A Pending CN115132901A (en) 2022-06-09 2022-06-09 Red light-near infrared light LED device and application thereof

Country Status (1)

Country Link
CN (1) CN115132901A (en)

Similar Documents

Publication Publication Date Title
EP2968972B1 (en) Quantum dot light-emitting diodes for phototherapy
US10244595B2 (en) Photonic engine system for actuating the photosynthetic electron transport chain
US11778953B2 (en) Light source for plant cultivation
US3670193A (en) Electric lamps producing energy in the visible and ultra-violet ranges
US20160014974A1 (en) Photonic engine system for actuating the photosynthetic electron transport chain
CN109550049A (en) Application of the carbon quantum dot-class graphite phase carbon nitride catalysis material in preparation sterilization and the drug for promoting skin scar healing
US12048853B2 (en) Light irradiation apparatus
CN115132901A (en) Red light-near infrared light LED device and application thereof
CN115224176A (en) Far-red light LED device and application thereof
KR101281528B1 (en) Method for growth promotion of fish using light wavelength
CN115109582B (en) Red light-near infrared light LED device and application thereof
JP2022515455A (en) LED lighting device with additional functions
CN113502160B (en) Blue light excited ultraviolet fluorescent powder and preparation method thereof
CN113563884B (en) Near infrared fluorescent material and preparation method thereof, and LED light-emitting device and preparation method thereof
EP4085750A1 (en) Light source for plant cultivation
CN103125411B (en) Fish growth adjustment lamp
CN202024186U (en) LED lamp beneficial to plant growth
CN112704735B (en) Inorganic ion mediated organic compound nano enzyme, preparation method and application
US20240350827A1 (en) Light irradiation apparatus
CN111394099B (en) Preparation and application of novel single-matrix double-light near-infrared tantalum-based pyrochlore material
CN108541658A (en) A kind of ecology pigeon cultural method and its foster dove device that uses
CN117224852A (en) Phototherapy device for inhibiting neuroinflammation and application
TWI839198B (en) Method for producing vitamin d content
CN1636576A (en) Application of bioactive glass in preparing medicine for treating gastroduodenal ulcer
KR101297823B1 (en) Pharmaceutical Compositions for Preventing or Treating Periodontal Diseases Comprising Photosensitizers and Pine Resin Extracts as an Active Ingredient Using LED irradiation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination