KR20180041540A - Upconversion nanophosphor having improved quantum yield - Google Patents
Upconversion nanophosphor having improved quantum yield Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 14
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims description 12
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 12
- 229910052772 Samarium Inorganic materials 0.000 claims description 12
- 229910052771 Terbium Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 10
- 229910052689 Holmium Inorganic materials 0.000 claims description 10
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- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
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- 238000004458 analytical method Methods 0.000 description 5
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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Abstract
Description
본 발명은 나노형광체에 관한 것으로, 보다 상세하게는 근적외선 영역의 빛을 가시광선으로 전환시키는 업컨버젼(upconversion, UC) 나노형광체에 관한 것이다.The present invention relates to a nanophosphor, and more particularly to an upconversion (UC) nanophosphor that converts light in the near infrared region into visible light.
발광 나노입자는 여기원(excitation source)으로부터 특정 파장의 광(light)을 흡수하여 여기 상태에 이르면, 에너지 밴드 갭에 따른 에너지에 해당하는 빛을 방출하는 나노물질이다. The light emitting nanoparticles are nanomaterials that emit light corresponding to the energy according to the energy band gap when they reach an excited state by absorbing light of a specific wavelength from an excitation source.
최근 발광 나노입자들은 낮은 독성, 광퇴색에 대한 저항, 근적외선의 투과가 뛰어나다는 등의 장점이 있어 바이오 이미징, 치료, 감지, 태양전지 및 분석 화학 등의 분야에서 중요한 재료로 사용되고 있다.Recently, luminescent nanoparticles have been used as important materials in fields of bioimaging, treatment, detection, solar cell and analytical chemistry because of their advantages such as low toxicity, resistance to light discoloration, and excellent transmission of near infrared rays.
특히, 란탄족 이온이 도핑된 발광 나노입자는 입자의 크기가 변하여도 발광 스펙트럼의 피크의 위치가 변하지 않는 유리한 특성이 있으며, 이는 란탄족 원소가 도핑된 발광 나노입자의 발광이 란탄족 원소의 4f 전자의 천이에 의한 4f-4f 천이 및 4f-5d 천이에 의해 일어나기 때문으로, 필요에 따라 발광 나노입자의 크기를 다양하게 조절하더라도 원하는 발광 파장을 유지할 수 있다는 장점이 있다.Particularly, the lanthanide ion-doped luminescent nanoparticles are advantageous in that the position of the peak of the luminescence spectrum does not change even when the size of the luminescent nanoparticle is changed. This is because the luminescence of the lanthanide element- 4f-4f transition and 4f-5d transition due to the electron transition, so that it is possible to maintain the desired emission wavelength even if the size of the light emitting nanoparticles is variously adjusted as necessary.
상기와 같은 발광 나노입자들은 일반적으로 자외선 또는 가시광선에 의해 여기될 때 발광하는 특성을 나타내며, 도핑하는 원소의 종류에 따라 근적외선 파장대의 빛에 의해 여기되어 가시광을 발광하는 특성을 나타낸다.The luminescent nanoparticles as described above generally exhibit luminescence characteristics when they are excited by ultraviolet rays or visible rays and exhibit a characteristic of emitting visible light by being excited by light of a near infrared ray wavelength band depending on the kind of doping element.
업컨버젼(Upconversion) 나노형광체와 관련해, 종래에는 란탄족 이온이 도핑된 NaYF4, NaGdF4 또는 NaLuF4 나노형광체 등에 관한 기술 내용이 개시된 바 있다.Related to the upconversion nano-phosphors, there have been disclosed the technical contents of NaYF 4 , NaGdF 4 or NaLuF 4 nano-phosphors conventionally doped with lanthanide ions.
상기한 불소 기반의 나노형광체는 불소를 포함하지 않는 나노형광체에 비하여 보다 높은 업컨버젼 발광 효율을 나타내며, 입방정 구조인 α상과 육방정 구조인 β상의 동질이상을 나타내는데, β상이 α상보다 우수한 업컨버젼 발광특성을 나타낸다.The fluorine-based nanophosphor exhibits higher up-conversion luminous efficiency as compared with a nano-fluorescent material containing no fluorine, and exhibits a homogeneous anomaly of a cubic phase and an cubic crystal structure, And shows conversion light emission characteristics.
하지만, 종래 기술에 따르면 α상으로부터 β상으로 상전이(phase transition)된 업컨버젼 나노형광체는 800 ℃ 이상의 고온의 유기 용매에서 공침법(co-precipitaion)을 통해 합성되었기 때문에 제조 공정이 어렵고 비경제적일 뿐만 아니라, 높은 합성 온도로 인해 나노입자의 뭉침 현상이 발생해 나노형광체의 입자크기가 증가하고, 증가된 입자크기로 인해 광(light)을 흡수할 수 있는 표면적이 작으며, 양자 수율이 낮아 발광 세기가 다소 떨어지는 문제점이 있다.However, according to the prior art, up-conversion nano-phosphors that have undergone a phase transition from an? Phase to? Phase are synthesized through co-precipitation in an organic solvent at a high temperature of 800 ° C or higher, In addition, due to the high synthesis temperature, the nanoparticles aggregate to increase the particle size of the nanophosphor, the surface area to absorb light due to the increased particle size is small, and the quantum yield is low There is a problem that the strength is somewhat deteriorated.
본 발명은 상기한 바와 같은 종래기술의 문제점을 해결하기 위해, NaAGdF4:B1, B2을 포함하는 불소 기반의 나노형광체의 결정상(α상에서 β상으로 상전이)을 제어하는 손쉬운 방법으로 개선된 양자 수율을 갖는 업컨버젼 나노입자와 이를 제조하는 방법에 관한 기술 내용을 제공하는 것을 그 목적으로 한다.The invention, NaAGdF 4] To solve the problems of the prior art as described above: an improved in an easy way to control the B 1, B 2 of the nano fluorescent material crystal phase of fluorine-based, including a (the phase transition to β phase on α) It is an object of the present invention to provide upconversion nanoparticles having a quantum yield and a method of manufacturing the nanoparticles.
상기한 바와 같은 기술적 과제를 달성하기 위해, 본 발명은, NaAGdF4:B1, B2 (단, 상기 A는 란탄족 원소이고, 상기 B1 및 B2는 서로 다른 희토류 원소임)에 Cr3+이 동시 도핑된(co-dopoed) 업컨버젼(upconversion, UC) 나노형광체를 제공한다.In order to achieve an aspect described above, the present invention, NaAGdF 4: B 1, B 2 Cr 3 a (where A is lanthanum group elements, and wherein B 1 and B 2 are different rare earth element-hydrogen) + ≪ / RTI > co-doped upconversion (UC) nano-phosphors.
또한, 상기 A는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm 및 Eu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 한다.A is one selected from the group consisting of Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm and Eu.
또한, 상기 B1 및 B2는 서로 상이하며 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 및 Lu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 한다.B 1 and B 2 are different from each other and are composed of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, And the like.
또한, 상기 나노형광체는 상기 Cr3+의 함량이 1 내지 30 mol%인 것을 특징으로 한다.In addition, the nanophosphor is characterized in that the content of Cr 3+ is 1 to 30 mol%.
또한, 상기 나노형광체는 750 내지 1500 nm 파장의 광(light)을 흡수하여 400 내지 700 nm 파장의 광을 방출하는 것을 특징으로 한다.The nano-phosphors absorb light having a wavelength of 750 to 1500 nm and emit light having a wavelength of 400 to 700 nm.
또한, 본 발명은, (a) A 전구체, Gd 전구체, B1 전구체, B2 전구체 및 Cr 전구체를 포함하는 전구체 혼합용액을 제조하는 단계(단, 상기 A는 란탄족 원소이고, 상기 B1 및 B2는 서로 다른 희토류 원소임); (b) 상기 단계(a)에서 제조한 전구체 혼합용액에 올레산(Oleic acid) 및 옥타데센(Octadecene)을 혼합하여 제1 혼합용액을 제조하는 단계; (c) 상기 단계(b)에서 제조한 제1 혼합용액에 불화나트륨(NaF) 및 수산화나트륨(NaOH)을 혼합하여 제2 혼합용액을 제조하는 단계; 및 (d) 상기 단계(c)에서 제조한 제2 혼합용액을 열처리한 후 알코올을 첨가하여 나노입자를 형성하는 단계를 포함하는 나노형광체의 제조방법을 제공한다.In addition, the present invention, (a) A precursor, Gd precursor, B 1 precursor, B 2, and step (where A is lanthanoids for preparing a precursor mixture comprising a precursor and Cr precursor, wherein B 1 and B 2 is a different rare earth element); (b) preparing a first mixed solution by mixing oleic acid and octadecene with the precursor mixture solution prepared in step (a); (c) mixing the first mixed solution prepared in the step (b) with sodium fluoride (NaF) and sodium hydroxide (NaOH) to prepare a second mixed solution; And (d) heat-treating the second mixed solution prepared in the step (c) and adding alcohol to form nanoparticles.
또한, 상기 A는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm 및 Eu로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 한다.A is at least one selected from the group consisting of Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm and Eu.
또한, 상기 B1 및 B2는 서로 상이하며 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 및 Lu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 한다.B 1 and B 2 are different from each other and are composed of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, And the like.
또한, 상기 단계 (d)는 100 내지 300 ℃의 온도로 열처리하는 것을 특징으로 한다.The step (d) is characterized in that the heat treatment is performed at a temperature of 100 to 300 ° C.
또한, 본 발명은 상기에 기재된 나노형광체를 반사물질로 포함하는 태양광전지를 제공한다.The present invention also provides a solar photovoltaic cell comprising the nanophosphor described above as a reflective material.
또한, 본 발명은 상기에 기재된 나노형광체를 포함하는 바이오 표지물질을 제공한다.The present invention also provides a bioabsorbable material comprising the above-described nanophosphor.
본 발명에 따른 업컨버젼 나노형광체는, NaAGdF4:B1, B2에 란탄족 원소와 Cr3+이 동시에 도핑되어, 나노형광체의 결정상을 입방정상에서 육방정상으로 상전이를 유도하고, Cr3+가 서로 다른 희토류(B1 및 B2)에 에너지를 전달하는 증감제(sensitizer)로 작용하며, 서로 이웃하는 Cr3+ 및 희토류의 이온간 거리가 짧아져, Cr3+ 및 희토류의 다중 포톤 흡수 기작(multi-photon process)에 의해 양자 수율이 20배 이상 향상되어 우수한 업컨버전 형광 특성을 나타낸다.Up-conversion nano fluorescent material according to the present invention, NaAGdF 4: B 1, the lanthanides and the Cr 3+ B 2 are doped at the same time, induce the phase transition to the normal hexagonal crystalline phase of the nano fluorescent material on the cubic crystal, and, a Cr 3+ It acts as a sensitizer that transfers energy to the different rare earths (B 1 and B 2 ), and the distance between adjacent ions of Cr 3+ and rare earths is shortened, so that Cr 3+ and rare- the quantum yield is improved by more than 20 times by the multi-photon process and exhibits excellent up-conversion fluorescence characteristics.
또한, 본 발명에 따른 업컨버전 나노형광체의 제조방법에 따르면, 저온에서도 육방정상이 우세한 나노형광체를 제조할 수 있을 뿐만 아니라, 입자의 뭉침을 저하시켜 입자의 크기가 작은 나노형광체를 제조할 수 있다.In addition, according to the method for producing an upconverted nano-phosphor according to the present invention, it is possible not only to produce a nano-fluorescent substance dominated by hexagonal phase even at a low temperature, but also to reduce the aggregation of particles to produce a nano- .
도 1은 다중 포톤 흡수 기작 매커니즘(multi-photon absorption process mechanism)을 개략적으로 나타내는 도면이다.
도 2는 실시예 3에 따른 나노형광체의 EDS 스펙트럼을 나타내는 도면이다.
도 3은 실시예 3에 따른 나노형광체의 입자구조를 나타내는 FE-SEM 이미지이다.
도 4는 실시예 1 내지 실시예 5에 따른 나노형광체의 XRD 패턴을 나타내는 도면이다.
도 5는 실시예 1 내지 실시예 5에 따른 나노형광체의 업컨버젼 발광세기를 나타낸 그래프이다.
도 6은 실시예 3에 따른 나노형광체의 업컨버젼 형광 스펙트럼을 나타내는 도면이다.
도 7은 실시예 3에 따른 나노형광체에 대한 업컨버젼 발광세기의 펌프파워에 대한 의존성을 나타내는 그래프이다.Figure 1 is a schematic representation of a multi-photon absorption process mechanism.
2 is a view showing an EDS spectrum of a nanophosphor according to Example 3. Fig.
3 is an FE-SEM image showing the particle structure of the nanophosphor according to Example 3. Fig.
4 is a view showing an XRD pattern of the nano-phosphors according to Examples 1 to 5. Fig.
5 is a graph showing up-conversion luminescence intensities of the nano-phosphors according to Examples 1 to 5.
6 is a view showing an up-conversion fluorescent spectrum of the nanophosphor according to Example 3. Fig.
7 is a graph showing the dependency of the upconversion luminous intensity on the pump power of the nanophosphor according to the third embodiment.
이하, 본 발명을 상세히 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명은, NaAGdF4:B1, B2 (단, 상기 A는 란탄족 원소이고, 상기 B1 및 B2는 서로 다른 희토류 원소임)에 Cr3+이 동시 도핑된(co-dopoed) 업컨버젼(upconversion, UC) 나노형광체를 제공한다.The invention, NaAGdF 4: B 1, B 2 (stage, and A is a lanthanide element, wherein B 1 and B 2 are different rare earth element-hydrogen) Cr 3+ is co-doped (co-dopoed) up to Thereby providing upconversion (UC) nano-phosphors.
상기 나노형광체는 A를 포함하여, 입자의 크기가 변하여도 발광 스펙트럼의 피크의 위치가 변하지 않는 특성을 나타낸다.The nanophosphor contains A and exhibits the property that the position of the peak of the emission spectrum does not change even when the size of the particle changes.
상기와 같은 특성을 나타낼 수 있도록 포함되는 A는 란탄족으로 분류되는 원소들을 바람직하게 포함할 수 있으며, 상기 란탄족 원소는 4f 전자의 전이에 의한 4f-4f 전이 및 4f-5d 전이에 의해 나노형광체의 발광이 일어나기 때문에, 상기 란탄족 이온을 포함하는 나노형광체는 입자의 크기가 변하여도 발광 스펙트럼의 피크의 위치가 변하지 않는 효과를 나타내 필요에 따라 나노형광체의 크기를 조절할 수 있는 특성을 부여할 수 있다.In order to exhibit the above-mentioned characteristics, A may preferably include elements classified as lanthanoid elements, and the lanthanide elements may be represented by 4f-4f transition and 4f-5d transition by transition of 4f electron, The nanophosphor containing the lanthanide ions exhibits the effect that the position of the peak of the luminescence spectrum is not changed even when the size of the nanopowder changes, and it is possible to give the property of controlling the size of the nanophosphor have.
상기 A는 바람직하게는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu 또는 이들의 혼합물을 란탄족 원소로 포함할 수 있다.The A may preferably include Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu or a mixture thereof as a lanthanide element.
또한, 상기 나노형광체는 포함되는 A의 몰분율에 따라서 나노형광체 입자의 크기가 달라질 수 있으며, 원하는 크기의 나노형광체 입자를 얻기 위해 적합한 이온을 선택하여 포함할 수 있다.Further, the size of the nanophosphor particles may be varied according to the mole fraction of A contained in the nanophosphor, and a suitable ion may be selected to obtain nanophosphor particles of a desired size.
아울러, 나노형광체는 Gd를 포함하여 자성을 띌 수 있으며, 자성에 의한 자기공명의 특성으로 인해, 광학적 이미지뿐만 아니라, 자기공명 이미지의 제공을 위한 용도로 사용될 수 있다.In addition, the nano-phosphors can be magnetized including Gd, and due to the magnetic resonance characteristics, they can be used not only for optical images but also for providing magnetic resonance images.
또한, 상기 나노형광체는 희토류 원소인 B1 및 B2를 포함할 수 있고, 상기 B1 및 B2는 서로 다른 원소를 포함한다.In addition, the nano-phosphors may include rare earth elements B 1 and B 2 , and B 1 and B 2 include different elements.
상기 나노형광체는 큰 흡수 단면적을 가지는 B1 또는 B2가 나노형광체에 도입되어, B1이 가해지는 근적외선 파장의 빛을 흡수하여 B2로 에너지를 전달하거나, 또는 B2가 근적외선 파장의 빛을 흡수하여 B1으로 에너지를 전달하여 업컨버젼 현상이 나타나므로 나노형광체에 포함될 수 있다.The nano fluorescent material is the B 1 or B 2 having a large absorption cross section introduced into the nano fluorescent material, B 1 is transferring energy to the B 2 absorbs light of near infrared wavelength is applied, or B 2 is a light of near infrared wavelength And the energy is transferred to B 1 by up-conversion phenomenon, so that it can be included in the nano-phosphors.
상기 B1 및 B2는 서로 상이한 원소로 구성되며 바람직하게는, 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 또는 Lu로 이루어진 군으로부터 선택되는 1종을 포함할 수 있다.B 1 and B 2 are different from each other and are preferably selected from the group consisting of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Or Lu. ≪ / RTI >
본 발명에 있어서, 상기한 나노형광체는 NaAGdF4:B1, B2에 Cr3+이 동시 도핑되어 종래에 불소 기반의 나노형광체가 나타내는 입방정상에서 육방정상으로 상전이를 유도하며, Cr3+이 Yb3+ 이온 및/또는 Er3+ 이온으로 에너지를 전달하는 증감제 역할을 수행하여 양자 수율이 20배 이상 향상된 특성을 보인다.In the present invention, the nano fluorescent material is NaAGdF 4: B 1, B 2 to the Cr 3+ is simultaneously doped and inducing phase transition to hexagonal top on the cubic crystal represented by the nano fluorescent material of fluorine based on the prior art, the Cr 3+ Yb 3+ ion and / or Er 3+ ion, and the quantum yield is improved by more than 20 times.
본 발명에 있어서 입방정상에서 육방정상으로 상전이는, 일례로, NaLuGdF4:Yb,Er,Cr3+의 조성을 가지는 업컨버젼 나노형광체의 경우, 먼저 Lu는 Na+, F-와 반응하여 α-NaLuF4 핵을 형성하고, α-NaLuF4 핵은 표면에 친유성(oleophilic)을 띄는 올레산 분자가 흡착되어 수용액 상에서 단분산(mono-disperse) 형태로 형성될 수 있다. In the present invention, for example, in the case of the upconversion nanophosphor having a composition of NaLuGdF 4 : Yb, Er, Cr 3+ , Lu reacts with Na + and F - to form α-NaLuF 4 And the α-NaLuF 4 nucleus can be formed into a mono-disperse form in an aqueous solution by adsorbing an oleophilic molecule having oleophilic surface on the surface.
상기 Cr3+ 이온의 반경은(r=0.62 Å) Lu3+ 이온의 반경(r=0.86 Å)보다 작으며, 이에 의해 격자 안에서 Cr3+ 이온에 의해 Lu3+ 이온의 치환(교체)이 발생하고, 다음 단계에서, 더 큰 이온반경을 가지는 Gd3 + 이온 (r=0.94 Å)은 Cr3 + 이온을 치환하며, 그 결과로, α상에서 β상으로 상전이가 발생할 수 있다. 이때, 특정크기를 가지는 α-NaLuGdCrF4 핵은 열역학적으로 불안정하며, 이로 인해 저온에서도 β-NaLuGdCrF4 형태로 전환이 가능하여, β상이 우세하게 나타나는 특성을 보인다.The radius of the Cr 3+ ion is smaller than the radius of the Lu 3+ ion (r = 0.86 Å) (r = 0.62 Å), whereby the substitution (replacement) of the Lu 3+ ion by the Cr 3+ ion in the lattice In the next step, the Gd 3 + ion (r = 0.94 Å) with a larger ionic radius replaces the Cr 3 + ion and, as a result, the phase transition from α phase to β phase can occur. At this time, the α-NaLuGdCrF 4 nucleus having a specific size is thermodynamically unstable and can be converted into β-NaLuGdCrF 4 form even at a low temperature, so that β phase is predominant.
이에 따라, 본 발명의 나노형광체는 Cr3+ 이온의 도핑을 통해 α상으로부터 β상으로의 상전이(phase transition)가 유도되어, 기존의 합성 온도(800 ℃ 이상)보다 훨씬 낮은 온도에서 합성되더라도 우수한 업컨버젼 특성을 가지는 β상을 지배적으로 포함할 수 있다.Accordingly, the nanophosphor of the present invention induces a phase transition from the alpha phase to the beta phase through doping of Cr 3+ ions, and is excellent even when synthesized at a much lower temperature than the conventional synthesis temperature (800 ° C or higher) And may predominantly include a? Phase having upconversion characteristics.
또한, 상기한 나노형광체의 양자 수율의 향상은 다중 포톤 흡수 기작(multi-photon absorption process)과 연관되어 있다(도 1).In addition, the improvement of the quantum yield of the nano-phosphors is associated with a multi-photon absorption process (Fig. 1).
일례로, NaLuGdF4:Yb,Er,Cr3+의 조성을 가지는 업컨버젼 나노형광체의 경우, Er3+ 이온은 바닥 상태 흡수(ground state absorption, GSA), 여기 흡수(excited state absorption, ESA) 및 크로스 완화 기작(cross realxation process)에 의해 여기 상태로 위치될 수 있다. For example, in the case of upconverted nano-phosphors having a composition of NaLuGdF 4 : Yb, Er, Cr 3+ , the Er 3+ ion can be used for ground state absorption (GSA), excited state absorption (ESA) May be placed in an excited state by a cross realization process.
Yb3+ 이온은 약 10,000 cm-1에 해당되는 단 하나의 에너지 갭을 가지며, 이 에너지 갭은 Cr3+:4T2g 및 Cr3+:4A2g(약 11,000 cm-1)사이의 에너지 갭과 가까워, Yb3+ 이온 및 Cr3+ 이온이 서로 수용체(acceptor)와 공여체(donor)로서 작용할 수 있다. 따라서 Cr3+ 이온이 Yb3+ 이온 및/또는 Er3+ 이온으로 에너지를 전달하는 증감제 역할을 함으로써 양자 수율을 개선하며, Cr3+ 이온 농도가 증가하여 서로 이웃하는 Cr3+ 이온 및 Yb3+ 이온 또는 Er3+ 이온의 이온거리를 짧게 하고, 이와 같은 개선된 양자 수율 및 짧은 이온거리에 의해 업컨버젼 효율이 향상된 특성을 보인다.The Yb 3+ ion has a single energy gap of about 10,000 cm -1 , which is the energy between Cr 3+ : 4 T 2 g and Cr 3+ : 4 A 2 g (about 11,000 cm -1 ) Gap, and Yb 3+ ions and Cr 3+ ions can act as acceptors and donors to each other. Therefore, Cr 3+ ions are Yb 3+ ions and / or Er 3+ acts as a sensitizer by which ions transfer energy and improve the quantum yield, Cr 3+ ion concentration is increased in the adjacent Cr 3+ ions and Yb The ion distance of the 3+ ion or the Er 3+ ion is shortened and the upconversion efficiency is improved by the improved quantum yield and the short ion distance.
본 발명에 따른 나노형광체는 상기한 바와 같은 바람직한 효과를 나타낼 수 있도록 도핑되는 Cr3 +의 함량이 1 내지 30 mol%(도펀트 함량기준)로 포함하도록 구성할 수 있다.The nanophosphor according to the present invention may be configured such that the content of doped Cr 3 + is in the range of 1 to 30 mol% (based on the dopant content) so as to exhibit the above-described preferable effect.
상기와 같이, Cr3+의 함량을 한정한 이유는 Cr3+이 1 mol% 미만으로 포함되면 향상된 상전이 효과를 기대하기 어려우며, 30 mol%를 초과하는 경우에는 Cr3+에 의한 호스트의 격자 왜곡이 심해지고 농도소광(concentration quenching)을 일으켜 나노형광체의 발광 세기가 감소될 수 있기 때문에 이와 같은 범위로 Cr3+을 포함하도록 구성할 수 있으며, 보다 바람직하게는 5 내지 25 mol% 함량으로 포함할 수 있다.As described above, the reason for limiting the content of Cr 3+ is Cr 3+ is 1 when containing less than mol% is difficult to expect an improved phase change effect, lattice strain of the host according to the Cr 3+ in the case of exceeding 30 mol% And the concentration of quenching may be reduced to decrease the luminescence intensity of the nano-fluorescent material. Therefore, Cr 3+ can be included in such a range, more preferably 5 to 25 mol% .
본 발명의 나노형광체는 750 내지 1500 nm 파장의 광(light)을 흡수하여 400 내지 700 nm 파장의 광을 방출할 수 있으며, 상기 나노형광체는 근적외선 파장의 광을 흡수하여 가시광선 파장의 광을 방출하는 업컨버젼 특성을 나타낼 수 있다.The nanofluorescent material of the present invention absorbs light having a wavelength of 750 to 1500 nm and emits light having a wavelength of 400 to 700 nm. The nanofluorescent material absorbs light having a near-infrared wavelength and emits light having a visible light wavelength The up-conversion characteristic can be shown.
상기한 바와 같은 본 발명에 따른 업컨버젼 나노형광체는, Cr3+이 동시 도핑됨으로써, 다중 포톤 흡수 기작(multi-photon absorption process)에 의해 양자 수율이 20배 이상 향상되어 업컨버젼 특성을 현저하게 증가시킬 수 있는 효과가 있다.As described above, the upconversion nano-phosphors according to the present invention are improved in the quantum yield by 20 times or more by the multi-photon absorption process due to simultaneous doping of Cr 3+ , There is an effect that can be made.
또한, 본 발명은 상기한 바와 같은 업컨버젼 나노형광체를 제조하기 위해서, (a) A 전구체, Gd 전구체, B1 전구체 B2 전구체 및 Cr 전구체를 포함하는 전구체 혼합용액을 제조하는 단계(단, 상기 A는 란탄족 원소이고, 상기 B1 및 B2는 서로 다른 희토류 원소임); (b) 단계(a)의 전구체 혼합용액에 올레산(Oleic acid) 및 옥타데센(Octadecene)을 혼합하여 제 1 혼합용액을 제조하는 단계; (c) 단계(b)의 제 1 혼합용액에 불화나트륨(NaF) 및 수산화나트륨(NaOH)을 혼합하여 제 2 혼합용액을 제조하는 단계; 및 (d) 단계(c)의 제 2 혼합용액을 열처리 후 알코올을 첨가하여 나노입자를 형성하는 단계를 포함하는 것을 특징으로 하는 나노형광체의 제조방법을 제공한다. The present invention also provides a method for producing an up-conversion nano-fluorescent substance comprising the steps of: (a) preparing a precursor mixed solution containing an A precursor, a Gd precursor, a B 1 precursor B 2 precursor, and a Cr precursor, A is a Lanthanon element, and B 1 and B 2 are different rare earth elements; (b) mixing a precursor mixture solution of step (a) with oleic acid and octadecene to prepare a first mixed solution; (c) mixing sodium fluoride (NaF) and sodium hydroxide (NaOH) in the first mixed solution of step (b) to prepare a second mixed solution; And (d) heat-treating the second mixed solution of step (c) and adding alcohol to form nanoparticles.
먼저, 단계(a)는 A 전구체, Gd 전구체, B1 전구체, B2 전구체 및 Cr 전구체를 포함하는 전구체 혼합용액을 제조하는 단계(단, 상기 A는 란탄족 원소이고, 상기 B1 및 B2는 서로 다른 희토류 원소임)이다.First, step (a) A precursor, Gd precursor, B 1 precursor comprising the steps of: preparing a precursor mixture containing a B 2 precursor and Cr precursor (but wherein A is a lanthanide element, wherein B 1 and B 2 Are different rare earth elements).
염산수용액에 A 산화물, Gd 산화물, B1 산화물, B2 산화물 및 Cr 산화물을 넣고 교반하여 교반용액을 제조할 수 있다. 교반용액의 색이 없어지면 알코올을 혼합하여 전구체 혼합용액을 제조할 수 있다.An A oxide, a Gd oxide, a B 1 oxide, a B 2 oxide and a Cr oxide are added to an aqueous hydrochloric acid solution and stirred to prepare a stirred solution. When the color of the stirring solution disappears, a mixed solution of the precursor can be prepared by mixing alcohol.
상기 A는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm 및 Eu로 이루어진 군으로부터 선택된 1종의 란탄족 원소일 수 있다.A may be a lanthanide element selected from the group consisting of Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm and Eu.
또한, 상기 B1 및 B2는 서로 상이한 원소를 포함하며, 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 또는 Lu로 이루어진 군으로부터 선택된 1종일 수 있다.B 1 and B 2 each include a different element and each of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Lu, and the like.
단계(b)는 단계(a)의 전구체 혼합용액에 올레산(Oleic acid) 및 옥타데센(Octadecene)을 혼합하여 제1 혼합용액을 제조하는 단계로, 상기 단계(a)의 전구체 혼합용액에 올레산 및 옥타데센을 첨가하고 교반하여 제1 혼합용액을 제조할 수 있다.The step (b) is a step of mixing a precursor mixture solution of step (a) with oleic acid and octadecene to prepare a first mixture solution, wherein oleic acid and / Octadecene is added and stirred to prepare a first mixed solution.
상기 단계(c)는 상기 제1 혼합용액에 불화나트륨(NaF) 및 수산화나트륨(NaOH)을 혼합하여 제2 혼합용액을 제조하는 단계로, 상기 단계(b)의 제1 혼합용액에 불화나트륨(NaF) 및 수산화나트륨(NaOH)을 첨가하고 교반하여 제2 혼합용액을 제조할 수 있다.Wherein the step (c) comprises mixing sodium fluoride (NaF) and sodium hydroxide (NaOH) in the first mixed solution to prepare a second mixed solution, and adding sodium fluoride NaF) and sodium hydroxide (NaOH) are added and stirred to prepare a second mixed solution.
단계(d)는 상기 제2 혼합용액을 열처리 후 알코올을 첨가하여 나노입자를 형성하는 단계로서, 상기 제2 혼합용액에 열을 가하고 알코올을 첨가하여 나노입자를 제조할 수 있다.Step (d) is a step of forming the nanoparticles by adding alcohol after the heat treatment of the second mixed solution, wherein the nanoparticles can be prepared by adding heat to the second mixed solution and adding alcohol thereto.
본 단계에서는 상기 나노형광체에 Cr3+ 이온이 도입되어 저온에서도 β상이 우세한 나노형광체를 합성할 수 있을 뿐만 아니라, 입자의 뭉침을 저하시키고 입자의 크기가 작은 나노형광체를 제조할 수 있다.At this stage, Cr 3+ ions are introduced into the nano-phosphors to synthesize nano-phosphors having a predominantly β-phase even at a low temperature. In addition, nano-phosphors having less particle aggregation and small particle sizes can be produced.
이를 위해, 본 단계에서 바람직하게는 100 내지 300 ℃에서 열처리 할 수 있으며, 더욱 바람직하게는 150 내지 250 ℃에서 열처리할 수 있다.In this step, heat treatment may be preferably performed at 100 to 300 ° C, more preferably 150 to 250 ° C.
본 발명은 상기와 같은 우수한 특성을 나타내는 나노형광체를 반사물질로 포함하는 태양광전지를 제공한다.The present invention provides a solar photovoltaic cell comprising a nano-fluorescent material exhibiting such excellent properties as a reflective material.
상기 나노형광체는 높은 업컨버젼 효율을 가져 태양전지 외부로 빠져나가는 손실광을 광흡수층으로 반사시킴과 동시에 나노형광체 입자에서 발광되는 광 또한 광흡수층으로 반사시키는 반사물질의 역할을 수행할 수 있어 효율이 높은 태양광전지를 구현할 수 있다.The nano-phosphors have a high up-conversion efficiency, thereby reflecting the loss of light that escapes to the outside of the solar cell to the light absorbing layer, and at the same time, the light emitted from the nano- A high solar photovoltaic cell can be realized.
또한, 본 발명은 상기와 같은 우수한 특성을 나타내는 나노형광체를 포함하는 바이오 표지물질(bio-probe)을 제공한다.The present invention also provides a bio-probe comprising the nanophosphor exhibiting the above-mentioned excellent properties.
상기 나노형광체는 높은 업컨버젼 세기를 가져, 표적 물질이 아주 소량으로 존재하는 경우에도 정밀한 검출, 정량 및 분리 등이 가능하여 다양한 표적 물질을 탐지할 수 있는 바이오 표지물질로 사용될 수 있다.The nano-phosphors have high up-conversion strength and can be used as bio-labeling materials capable of precisely detecting, quantifying and separating even if a target substance exists in a very small amount and detecting various target substances.
이때, 상기 나노형광체는 소정 기판 상에 부착되는 형태인 바이오 표지물질의 형태일 수 있으며, 항체 등의 표적지향성 물질이 결합될 수 있는 링커(linker)로써 포함될 수 있고, 이외의 공지된 다양한 형태의 바이오 표지물질 제조에 활용이 가능하다.At this time, the nanophosphor may be in the form of a bio-labeling substance attached on a predetermined substrate, and may be included as a linker to which a target-directing substance such as an antibody can be bound. In addition, It can be used to manufacture bio-labeling materials.
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명하도록 한다. 제시된 실시예는 본 발명의 구체적인 예시일 뿐이며, 본 발명의 범위를 제한하기 위한 목적으로 제공되는 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The embodiments presented are only a concrete example of the present invention and are not provided for the purpose of limiting the scope of the present invention.
<실시예 1> ≪ Example 1 >
전구체인 LnCl3(Ln=Lu, Gd, Yb, Er 및 Cr)을 제조하기 위하여, H2O:HCl= 2:1 부피비의 진한염산에서 70 ℃에서 3 시간 동안 Ln2O3를 교반하였다. 혼합용액의 색이 없어지기 시작하면 혼합용액에 메탄올을 첨가하여 LnCl3 전구체를 얻었다.To prepare the precursor LnCl 3 (Ln = Lu, Gd, Yb, Er and Cr), Ln 2 O 3 was stirred at 70 ° C in H 2 O: HCl = 2: 1 volume ratio of concentrated hydrochloric acid for 3 hours. When the color of the mixed solution began to disappear, methanol was added to the mixed solution to obtain a precursor of LnCl 3 .
다음 단계에서, LnCl3 전구체, 올레산 및 옥타데센을 첨가하여 격렬하게 교반하고 NaF 및 NaOH 용액을 첨가하여 Cr3+의 함량이 5 mol%로 첨가된 혼합용액을 제조하였다. 혼합용액을 60 mL Teflon-lined 오토클레이브에 옮겨 밀봉한 후 200 ℃에서 24시간 동안 반응시켰다.In the next step, LnCl 3 precursor, oleic acid and octadecene were added and vigorously stirred. NaF and NaOH solutions were added to prepare a mixed solution containing 5 mol% of Cr 3+ . The mixed solution was transferred to a 60 mL Teflon-lined autoclave, sealed, and reacted at 200 ° C for 24 hours.
그 후, 이소프로판올을 첨가하여 나노형광체 입자를 침전시켰다. 침전물을 원심분리하여 수집하고, 이소프로판올을 이용하여 세척하였다. 진공오븐에서 건조하여 5 mol%의 함량으로 Cr3+이 도핑된 NaLuGdF4:Yb,Er를 수득하였다.Thereafter, isopropanol was added to precipitate the nanophosphor particles. The precipitate was collected by centrifugation and washed with isopropanol. And dried in a vacuum oven to obtain Cr 3+ -doped NaLuGdF 4 : Yb, Er in an amount of 5 mol%.
<실시예 2>≪ Example 2 >
Cr3+이 10 mol%로 첨가되는 것을 제외하고는 실시예 1과 동일한 방법으로 10 mol%의 함량으로 Cr3+이 도핑된 NaLuGdF4:Yb,Er를 수득하였다.To give a Yb, Er: Cr 3+ is in Example 1 in the same manner as is the Cr 3+ in an amount of 10 mol% doping NaLuGdF 4 except that the addition of a 10 mol%.
<실시예 3>≪ Example 3 >
Cr3+이 15 mol%로 첨가되는 것을 제외하고는 실시예 1과 동일한 방법으로 15 mol%의 함량으로 Cr3+이 도핑된 NaLuGdF4:Yb,Er를 수득하였다.To give a Yb, Er: Cr 3+ 15 except that the addition of a mol% in Example 1 and a Cr 3+ doped in an amount of 15 mol% in the same manner NaLuGdF 4.
<실시예 4><Example 4>
Cr3+이 20 mol%로 첨가되는 것을 제외하고는 실시예 1과 동일한 방법으로 20 mol%의 함량으로 Cr3+이 도핑된 NaLuGdF4:Yb,Er를 수득하였다.To give a Yb, Er: Cr 3+ is in the example 1 and the Cr 3+ is doped in an amount of 20 mol% in the same manner NaLuGdF 4 except that the addition of a 20 mol%.
<실시예 5>≪ Example 5 >
Cr3+이 25 mol%로 첨가되는 것을 제외하고는 실시예 1과 동일한 방법으로 25 mol%의 함량으로 Cr3+이 도핑된 NaLuGdF4:Yb,Er를 수득하였다.Cr 3+ 25 except that the addition of a mol% and has a Cr 3+ doped in an amount of 25 mol% in the same manner as in Example 1 NaLuGdF 4: to give a Yb, Er.
<비교예><Comparative Example>
Cr3+을 포함하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 나노형광체입자를 합성하였다.Nano-sized phosphor particles were synthesized in the same manner as in Example 1, except that Cr 3+ was not included.
<실험예 1> 업컨버젼 나노형광체의 성분 분석<Experimental Example 1> Analysis of components of the upconverted nano-phosphor
본 발명의 실시예 3에 따른 나노형광체의 성분을 분석하기 위하여 에너지 분산형 X-선 감지기를 이용하여 에너지 분산형 X-선 발광 스펙트럼(energy dispersive x-ray emission spectra, EDS)을 측정하고 그 결과를 도 2에 나타내었다.The energy dispersive X-ray emission spectroscopy (EDS) was measured using an energy dispersive X-ray detector in order to analyze the components of the nano-phosphor according to Example 3 of the present invention, Is shown in Fig.
도 2에 나타난 바와 같이, 실시예 3에 따른 나노형광체는 Cr3+이 혼입되어 있음을 확인할 수 있으며, NaLuGdF4 호스트에 Cr3+이 도핑되어 있음을 확인할 수 있다.As shown in FIG. 2, it can be confirmed that Cr 3+ is incorporated in the nanophosphor according to Example 3, and that Cr 3+ is doped in the NaLuGdF 4 host.
<실험예 2> 업컨버젼 나노형광체의 입자 구조 분석<Experimental Example 2> Analysis of Particle Structure of Upconverted Nano Phosphor
실시예 3에 따른 나노형광체의 입자의 구조를 분석하기 위하여 전계 방출 전자 현미경(FE-SEM)을 이용하여 나노형광체의 미세 구조를 관찰하였으며, 나노형광체의 입자 구조는 도 3에 나타내었다.In order to analyze the structure of the nanoporous phosphor according to Example 3, the microstructure of the nanoporous phosphor was observed using a field emission electron microscope (FE-SEM), and the particle structure of the nanoporous phosphor was shown in FIG.
도 3에 나타난 바와 같이, Cr3+이 15 mol% 함량으로 도핑된 나노형광체는 작은 정육면체 및 육각형 입자의 형태를 나타냄을 확인할 수 있다.As shown in FIG. 3, it can be seen that the nanophosphor doped with Cr 3 + in an amount of 15 mol% exhibits small cube shape and hexagonal particle shape.
<실험예 3> Cr≪ Experimental Example 3 > Cr 3+3+ 이온 농도에 따른 상전이 상태 분석 Analysis of phase transition according to ion concentration
실시예 1 내지 실시예 5에 따른 나노형광체의 상전이 상태를 분석하기 위해 X-ray 회절계를 이용하여 XRD(X-ray powder diffraction) 패턴을 측정하고 그 결과 값을 도 4에 나타내었다.X-ray powder diffraction (XRD) patterns were measured using an X-ray diffractometer to analyze the phase transition states of the nano-phosphors according to Examples 1 to 5, and the results are shown in FIG.
도 4에 나타난 바와 같이, 낮은 Cr3+ 이온의 함량에서, α상(JCPDS-27-0725)의 나노형광체와 β상(JCPDS-27-0726)의 나노형광체가 혼합되어 있다는 것을 확인할 수 있다.As shown in FIG. 4, it can be seen that the nanophosphor of the alpha phase (JCPDS-27-0725) and the nanophosphor of the beta phase (JCPDS-27-0726) are mixed at a low Cr 3+ ion content.
또한, Cr3+ 이온의 함량이 증가할수록 β상의 나노형광체가 지배적으로 형성됨을 확인할 수 있다.In addition, it can be confirmed that as the content of Cr 3+ ions increases, a nano-fluorescent substance of β-phase is predominantly formed.
XDR 패턴에서 낮은 회절 각도로 이동하는 피크를 관찰할 수 있으며, 이는 호스트 격자 내에서 Cr3+ 이온이 Gd3+ 이온에 의해 치환되며 단위 격자(unit cell)의 부피가 팽창되어 나타나는 결과임을 확인할 수 있다.We can observe a peak moving at a low diffraction angle in the XDR pattern, which is the result of the substitution of the Cr 3+ ion by the Gd 3+ ion in the host lattice and the expansion of the unit cell volume have.
Cr3+ 이온들은 큰 전기음성도(1.6 eV)를 가져 NaLuGdF4:Yb,Er과 빠르게 반응하므로, 일시적으로 존재하는 상(temporary phase) 또는 2차상(minor phase)을 형성하며, 이러한 상은 도 4에 별 모양으로 표시한 피크(2θ= 19.17ㅀ, 22.46ㅀ, 31.89ㅀ 및 54.81ㅀ) 각각에 대응하는 (011), (002), (111) 및 (004)면을 가지는 Na3CrF6 상으로 나타나고, 그 피크 강도는 Cr3+ 이온의 농도가 증가할수록 함께 증가하는 것으로 확인되었다.Cr 3+ ions react with NaLuGdF 4 : Yb, Er with a large electronegativity (1.6 eV), forming a temporary or minor phase that is temporarily present, a peak (2θ = 19.17 DEG, 22.46 DEG, 31.89 DEG and 54.81 DEG) indicated by a star in the Na 3 CrF 6 phase having a (011), (002), (111) and (004) plane corresponding to each , And the peak intensity was found to increase with increasing Cr 3+ ion concentration.
<실험예 4> Cr<Experimental Example 4> 3+3+ 이온 농도에 따른 업컨버젼 발광 세기의 영향 분석 Analysis of influence of upconversion luminescence intensity on ion concentration
본 발명의 실시예 1 내지 실시예 5 및 비교예에 따른 나노형광체의 업컨버젼 발광세기를 측정하기 위하여, 형광 분광계를 이용하여 업컨버젼 발광 세기를 측정하고 그 결과 값을 도 5에 나타내었다.In order to measure the up-conversion luminescence intensities of the nano-phosphors according to Examples 1 to 5 and Comparative Examples of the present invention, up-conversion luminescence intensity was measured using a fluorescence spectrometer and the results are shown in Fig.
도 5에 나타난 바와 같이, Cr3+ 이온의 함량이 15 mol%일 때, 업컨버젼 발광 세기가 최대 값을 가지는 것을 확인할 수 있다.As shown in FIG. 5, when the content of Cr 3+ ions is 15 mol%, it can be confirmed that the intensity of the up-conversion luminescence has a maximum value.
그러나, Cr3+ 이온의 함량이 보다 증가할 경우, Cr3+ 이온에 의해 격자 왜곡증가해 희토류 이온의 공간 분포에 영향을 미치고 농도 소광(concentration quenching)을 일으켜 형광 강도를 감소시키는 것으로 확인되었다.However, when the content of Cr 3+ ions is increased, the lattice distortion is increased by Cr 3+ ions, which affects the spatial distribution of rare earth ions and causes concentration quenching, thereby reducing the fluorescence intensity.
<실험예 5> 업컨버젼 나노형광체의 업컨버젼 발광 스펙트럼 측정EXPERIMENTAL EXAMPLE 5 Up-Conversion Emission Spectrum Measurement of Upconverted Nano-Phosphor
본 발명의 실시예 3에 따른 나노형광체의 업컨버젼 발광 스펙트럼을 측정하기 위하여, 형광 분광계를 이용하여 업컨버젼 발광 스펙트럼을 측정하고 그 결과 값을 도 6에 나타내었다.In order to measure the up-conversion luminescence spectrum of the nano-phosphor according to Example 3 of the present invention, an up-conversion luminescence spectrum was measured using a fluorescence spectrometer, and the results are shown in Fig.
도 6에 나타난 바와 같이, Cr3+이 도핑된 업컨버젼 나노형광체는 근적외선 파장에서 발광을 나타냄을 확인할 수 있다.As shown in FIG. 6, it can be confirmed that the upconverted nano-fluorescent material doped with Cr 3+ shows luminescence at a near-infrared wavelength.
파장 980 nm의 빛에 의한 여기 하에서, 각각 2H9/2→4I15/2, 2H11/2→4I15/2, 4S3/2→4I15/2 및 4F9/2→4I15/2 Er3+ 전이에 해당하는 410, 522, 540, 및 655 nm에서 발광이 나타나는 것으로 확인되었다.Under excitation by light with a wavelength of 980 nm, each 2 H 9/2 → 4 I 15/2, 2 H 11/2 → 4 I 15/2, 4 S 3/2 → 4 I 15/2 and 4 F 9 / 2 → 4 I 15 / 2R 3+ transition at 410, 522, 540, and 655 nm, respectively.
<실험예 6> 업컨버젼 나노형광체의 업컨버젼 세기와 펌프파워의 상관성 분석Experimental Example 6 Analysis of Correlation between Upconversion Intensity and Pump Power of Upconverted Nano Phosphor
실시예 3에 따른 나노형광체의 업컨버젼 세기와 펌프파워의 상관성을 분석하기 위하여, 형광 분광계를 이용하여 업컨버젼 발광을 측정하고 펌프파워의 상관성을 log-log plot 분석하여 도 7에 나타내었다. 이때, 업컨버젼 세기(I) 및 펌프파워(P)의 상관성은 I∝Pn 과 같이 나타낼 수 있으며, 상기 n은 나노형광체를 여기시키기 위해 필요한 펌핑 광자수(pumping photons)이다.In order to analyze the correlation between the upconversion intensity and the pump power of the nano-phosphors according to Example 3, up-conversion luminescence was measured using a fluorescence spectrometer, and the correlation of the pump power was analyzed by a log-log plot. At this time, the correlation of the upconversion intensity I and the pump power P can be expressed as IαP n , where n is the pumping photons necessary for exciting the nanophosphor.
도 7에 나타난 바와 같이, n값은 낮은 펌프파워에서 녹색 및 적색 방출에 대해 각각 2.6 및 2.9 임을 확인할 수 있으며, 3에 가까운 수치가 나타나 낮은 펌프파워에서의 업컨버젼 기작에 3개의 포톤이 관여하고 있음을 확인할 수 있었다.As can be seen in Figure 7, the n values are 2.6 and 2.9 for green and red emissions at low pump power, respectively, with values approaching 3 indicating that three photons are involved in the upconversion mechanism at low pump power .
반면, 4F7/2 여기 상태의 업컨버젼 프로세스와 선형 감쇠(linear decay) 간의 경쟁에 기인해, 높은 펌프파워에서 n값은 녹색 및 적색 방출에 대해 각각 1.1 및 1.3으로 감소됨을 확인할 수 있었다.On the other hand, due to competition between the 4 F 7/2 excited up-conversion process and linear decay, the n values at high pump power were reduced to 1.1 and 1.3 for green and red emissions, respectively.
<실험예 7> 업컨버젼 나노형광체의 양자 수율 측정EXPERIMENTAL EXAMPLE 7 Measurement of Quantum Yield of Upconverted Nano-Phosphor
실시예 3에 따른 나노형광체의 양자 수율(나노형광체에 흡수된 여기광의 광양자 수에 대한 나노형광체로부터 방출된 광의 광양자 수의 비율)을 측정하기 위하여, 나노형광체의 여기광을 분광 형광계를 이용하여 측정하고, 나노형광체로부터 방출된 광을 황산바륨으로 코팅된 적분구 내에서 다중 반사시켜 방출된 광의 광양자 수를 검출하여 나노형광체의 양자 수율을 측정하였다. 참고로, 여기광은, Nd: YAG 레이저(Spectra Physics, Model Millennia)에 의해 펌핑된 Ti-S 레이저(Spectra Physics, Model 3900S)의 파장 980 nm의 빛을 이용하였다.In order to determine the quantum yield of the nanophosphor according to Example 3 (the ratio of the number of photons of the light emitted from the nanophosphor to the number of photons of the excited light absorbed in the nanophosphor), the excitation light of the nanophosphor was measured using a spectrophotometer And the quantum yield of the nano-phosphors was measured by detecting the number of photons of the emitted light by multiply reflecting the light emitted from the nano-phosphors in an integrating sphere coated with barium sulfate. For reference, the excitation light was a 980 nm wavelength light of a Ti-S laser (Spectra Physics, Model 3900S) pumped by a Nd: YAG laser (Spectra Physics, Model Millennia).
양자 수율을 측정한 결과, 실시예 3에 따른 방법에 의해 제조한 나노형광체의 양자 수율은 7.6%로 확인되었으며, Cr3+이 도핑되지 않은 비교예의 나노형광체에 비하여 양자 수율이 현저히 향상된 것으로 확인되었다. As a result of measuring the quantum yield, it was confirmed that the quantum yield of the nanophosphor prepared by the method according to Example 3 was 7.6%, and it was confirmed that the quantum yield was significantly improved as compared with the nanophosphor of the comparative example not doped with Cr 3+ .
Claims (11)
상기 A는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm 및 Eu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 하는 나노형광체.The method according to claim 1,
Wherein A is one selected from the group consisting of Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm and Eu.
상기 B1 및 B2는 서로 상이하며 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 및 Lu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 하는 나노형광체.The method according to claim 1,
Wherein B 1 and B 2 are different from each other and are selected from the group consisting of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 1 >.
상기 Cr3+의 함량이 1 내지 30 mol%인 것을 특징으로 하는 나노형광체.The method according to claim 1,
Wherein the content of Cr 3+ is 1 to 30 mol%.
750 내지 1500 nm 파장의 광(light)을 흡수하여 400 내지 700 nm 파장의 광을 방출하는 것을 특징으로 하는 나노형광체.The method according to claim 1,
Wherein the nanoporous material absorbs light having a wavelength of 750 to 1500 nm and emits light having a wavelength of 400 to 700 nm.
(b) 상기 단계(a)에서 제조한 전구체 혼합용액에 올레산(Oleic acid) 및 옥타데센(Octadecene)을 혼합하여 제1 혼합용액을 제조하는 단계;
(c) 상기 단계(b)에서 제조한 제1 혼합용액에 불화나트륨(NaF) 및 수산화나트륨(NaOH)을 혼합하여 제2 혼합용액을 제조하는 단계; 및
(d) 상기 단계(c)에서 제조한 제2 혼합용액을 열처리한 후 알코올을 첨가하여 나노입자를 형성하는 단계를 포함하는 나노형광체의 제조방법.(a) preparing a precursor mixture solution comprising an A precursor, a Gd precursor, a B 1 precursor, a B 2 precursor and a Cr precursor, wherein A is a lanthanide element, and B 1 and B 2 are different rare earths Circle;
(b) preparing a first mixed solution by mixing oleic acid and octadecene with the precursor mixture solution prepared in step (a);
(c) mixing the first mixed solution prepared in the step (b) with sodium fluoride (NaF) and sodium hydroxide (NaOH) to prepare a second mixed solution; And
(d) heat-treating the second mixed solution prepared in step (c), and adding alcohol to form nanoparticles.
상기 A는 Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm 및 Eu로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 나노형광체의 제조방법.The method according to claim 6,
Wherein A is at least one selected from the group consisting of Y, Tb, Dy, Ho, Tm, Lu, La, Ce, Pr, Nd, Pm, Sm and Eu.
상기 B1 및 B2는 서로 상이하며 각각 Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, 및 Lu로 이루어진 군으로부터 선택된 1종인 것을 특징으로 하는 나노형광체의 제조방법.The method according to claim 6,
Wherein B 1 and B 2 are different from each other and are selected from the group consisting of Yb, Er, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Wherein the nanoporous phosphor is one species.
상기 단계 (d)는 100 내지 300 ℃의 온도로 열처리하는 것을 특징으로 하는 나노형광체의 제조방법.The method according to claim 6,
Wherein the step (d) is a heat treatment at a temperature of 100 to 300 ° C.
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