Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2019/020661
Kind Code:
A1
Abstract:
The present invention relates to an agriculture composition comprising at least one phosphor.

Inventors:
OKURA HIROSHI (JP)
DERTINGER STEPHAN (DE)
SUZUKI RYUTA (JP)
AZUMA KAZUHISA (JP)
NISHIHARA EIJI (JP)
ISHIGAKI TADASHI (JP)
OHMI KOUTOKU (JP)
Application Number:
PCT/EP2018/070101
Publication Date:
January 31, 2019
Filing Date:
July 25, 2018
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
MERCK PATENT GMBH (DE)
International Classes:
A01N59/00; A01P15/00; C09K11/00
Foreign References:
Other References:
MINA M. MEDIC ET AL: "Deep-Red Emitting Mn 4+ Doped Mg 2 TiO 4 Nanoparticles", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 119, no. 1, 23 December 2014 (2014-12-23), pages 724 - 730, XP055505537, ISSN: 1932-7447, DOI: 10.1021/jp5095646
WEI LI ET AL: "Phytotoxicity, Uptake, and Translocation of Fluorescent Carbon Dots in Mung Bean Plants", ACS APPLIED MATERIALS & INTERFACES, vol. 8, no. 31, 26 July 2016 (2016-07-26), US, pages 19939 - 19945, XP055505409, ISSN: 1944-8244, DOI: 10.1021/acsami.6b07268
JUANJUAN PENG ET AL: "Upconversion nanoparticles dramatically promote plant growth without toxicity", NANO RESEARCH, vol. 5, no. 11, 2 October 2012 (2012-10-02), CN, pages 770 - 782, XP055505420, ISSN: 1998-0124, DOI: 10.1007/s12274-012-0261-y
XIN PANG ET AL: "Application of rare-earth elements in the agriculture of China and its environmental behavior in soil.", ENVIRON SCI POLLUT RES INT., 31 December 2002 (2002-12-31), XP055505528, Retrieved from the Internet [retrieved on 20180907]
Download PDF:
Claims:
Patent Claims

An agriculture composition comprising at least one phosphor, wherein the phosphor has a peak emission light wavelength in the range of 430 - 500 nm or 600 - 730 nm.

The agriculture composition according to claim 1 further comprising an additive, wherein the additive is at least one selected from the group consisting of a spreading agent or a surface treatment agent.

The agriculture composition according to claim 1 or 2 further comprising at least one solvent, wherein

the solvent comprises at least one selected from the group of water and organic solvent, and

preferably the organic solvent comprises at least one selected from the group of alcohol solvent and ether solvent.

The agriculture composition according to claim 3, wherein

the mass ratio of the solvent to the total mass of the agriculture composition is 70 - 99.95 mass %, and

the mass ratio of the phosphors to the total mass of the agriculture composition is 0.05 - 30 mass %.

The agriculture composition according to one or more of claims 1 to 4, wherein

the phosphor is at least one selected from the group consisting of an inorganic phosphor or an organic phosphor,

the inorganic phosphor is at least one selected from the group consisting of sulfides, thiogallates, nitrides, oxy-nitrides, silicates, metal oxides, apatites, phosphates, selenides, borates and carbon materials, and

the organic phosphor is at least one selected from the group consisting of fluorescein derivative, rhodamine derivative, coumarin derivative, pyrene derivative, cyanine derivative, perylene derivative, and di-cyano-methylene derivative.

5

6. The agriculture composition according to one or more of claims 1 to 5, wherein

the phosphor is at least one metal oxide phosphor represented by following formula (I),

10

C1 pC2qC3rC4sOt:MC - (I)

wherein C1 is a monovalent cation which is at least one selected from the group consisting of Li, Na, K, Rb and Cs,

^ C2 is a divalent cation which is at least one selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn, C3 is a trivalent cation which is at least one selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, Sm, Al, Ga, and In,

C4 is a tetravalent cation which is at least one selected from the

20

group consisting of Si, Ti, and Ge,

MC is a metal cation which is at least one selected from the group consisting of Cr3+, Eu2+, Mn2+, Mn4+, Fe3+, and Ce3+, and p, q, r, s and t are integers on or more than 0, satisfying that

25 (1 p+2q+3r+4s)=2t, and at least one of p, q, r and s is on or more than

1 .

7. The agriculture composition according to one or more of claims 1 to 6, wherein

the phosphor is at least one inorganic phosphor,

the inorganic phosphor is at least one selected from the group consisting of Cr activated metal oxide phosphors represented by following formulae (II) or (III) and Mn activated metal oxide phosphors represented by following formulae (IV) or (V), AxByOz:Cr3+ - (II)

wherein A is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm, B is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, and In; x and y are integers; x≥0; y≥ 1 ; and 1 .5(x+y) = z; XaZbOc:Cr3+ - (III)

wherein X is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; a and b are integers; b≥0; a≥1 ; and (a+1 .5b) = c; C2qC3rC4sOt:MC2+ - (IV)

wherein MC2+ is a divalent metal cation selected from "Eu2+", "Mn2+", or "Eu2+,Mn2+";

the definitions of C2, C3, C4, q, r, s and t are independently same to claim 6;

wherein the definitions of C2, C3, C4, q, r, s and t are independently same to claim 6.

8. The agriculture composition according to one or more of claims 1 to 7, wherein

the phosphor is at least one inorganic phosphor, and

the inorganic phosphor is at least one selected from the group consisting of AI2O3:Cr3+, Y3AI5Oi2:Cr3+, MgO:Cr3+, ZnGa2O4:Cr3+, MgAI2O4:Cr3+, Sr3MgSi2O8:Mn4+, Sr2MgSi2O7:Mn4+, SrMgSi2O6:Mn4+, Mg2SiO4:Mn2+, BaMg6Ti6Oi9:Mn4+, Mg2TiO4:Mn4+, Li2TiO3:Mn4+, CaAh2Oi9:Mn4+, ZnAI2O4:Mn2+, LiAIO2:Fe3+, LiAI5O8:Fe3+,

NaAISiO4:Fe3+, MgO:Fe3+, Mg8Ge2OnF2:Mn4+, CaGa2S4:Mn2+, Gd3Ga5Oi2:Cr3+, Gd3Ga5Oi2:Cr3+,Ce3+,

(Ca,Ba,Sr)MgSi2O6:Eu2+,Mn2+, (Ca,Ba,Sr)2MgSi2O7:Eu2+,Mn2+, (Ca,Ba,Sr)3MgSi2O8:Eu2+,Mn2+, ZnS, InP/ZnS, CulnS2, CulnSe2, CulnS2/ZnS and carbon quantum dot.

9. The agriculture composition according to one or more of claims 1 to 8, further comprising at least one selected from the group consisting of an adjuvant, a dispersant, a surfactant, a fungicide, an

antimicrobial agent, and an antifungal agent.

10. A method for manufacturing the agriculture composition according to one or more of claims 1 to 9, comprising adding at least one phosphor into a base composition, wherein

the base composition comprises at least one solvent,

the solvent comprises at least one selected from the group of water and organic solvent, and

preferably the organic solvent comprises at least one selected from the group of alcohol solvent and ether solvent.

1 1 .The method for manufacturing an agriculture composition according to claim 10, wherein the base composition is at least one selected from the group consisting of a pesticide formulation and a fertilizer formulation.

12. A method comprising applying the agriculture composition according to one or more of claims 1 to 1 1 , to the surface of a plant leaves.

13. A method for producing or enhancing a photosynthesis of one or more plant, by applying method according to claim 12.

14. The method for producing or enhancing a photosynthesis of one or more plant according to claim 13, wherein the average amount of the agriculture composition to be applied to the surface of the plant leaves is 0.0005 - 0.1 mL/cm2 of the surface

15. The method for producing or enhancing a photosynthesis of one or more plant according to claim 13 or 14, wherein

the agriculture composition is applied to the surface of the plant by spraying, watering, dropping, dipping, coating or combination of thereof.

0

16. The method for producing or enhancing a photosynthesis of one or more plant according to one or more of claims 13 to 15, wherein the agriculture composition is applied one or more times during the c growing season of the plant.

0

5

0

5

Description:
Composition

Field of the Invention

The present invention relates to an agriculture composition, a method manufacturing thereof, a method applying thereof to the surface of a plant leaves, a method producing a plant, and a method enhancing a

photosynthesis of a plant.

0 Background Art

JP 2007-135583 A mentions an organic dye having a peak wavelength at 613 nm and suggestion to use it with a thermoplastic resin as an agriculture film.

5

A polypropylene film containing an organic dye with peak light emission wavelength at 592 nm is disclosed in WO 1993/009664 A1 .

JP H09-249773 A mentions an organic dye having peak light wavelength ^ at 592 nm and a suggestion to use it with a polyolefin resin as an

agriculture film.

A combination of an ultraviolet light emitting diode, blue, red, yellow light 5 emitting diodes for green house light source is disclosed in JP 2001 -28947 A.

JP 2004-1 13160 A discloses a plant growth kit with a light emitting diode Q light source containing blue and red light emitting diodes.

(Ba,Ca,Sr)3MgSi2O8:Eu 2+ ,Mn 2+ phosphor and a suggestion to use it as an agricultural lamp are described on Non Patent Literature 1 .

A method applying composition including specific particulate materials to the surface of crop is described on EP 101 1309B1 . Patent Literature

1 . JP 2007-135583A

2. WO 1993/009664 A1

3. JP H09-249773A

4. JP 2001 -28947A

5. JP 2004-1 13160A

6. EP 101 1309B1 Non Patent Literature

7. "Analysis of (Ba,Ca,Sr)3MgSi2O8:Eu 2+ ,Mn 2+ phosphors for application in solid state lighting", Han et al., Journal of Luminescence (2014), vol. 148, p1-5

Summary of the invention

The inventors thought the wavelength by the natural light and an artificial light (e.g., a fluorescent lamp) is not optimal for growing plants, and an agriculture composition is useful which convert light and emit light with peak wavelength in the range of 430 - 500 nm or 600 - 730 nm.

Depending on a plant grow stage, an optimal wavelength changes. So, the inventors thought spot and/or tentative implementation of such wavelength converting measure is useful for agriculture, without introducing specific facilities.

Some above mentioned prior arts describe light conversion sheets and optical devices. But with using those ways, making spot environment is difficult, and the light conversion sheet and optical device needs to be replaced in the case necessary e.g., different wavelength is desired.

To solve those problems, the inventors conducted intensive researches and achieved an agriculture composition comprising a phosphor(s) which is useful for plant photosynthesis. For those purposes, a phosphor(s) is desirable which exhibits good UV stability, good color fastness, good color stability, and less concentration quenching.

One aspect of this invention provides applying method of an agriculture composition to the surface of a plant leaves. So, an embodiment of this

5

composition which adhere to the surface is useful. For example, a composition comprising a phosphor(s) and a spreading agent(s) is useful. Applying measure of the composition is not limited to liquid state. In the case the composition is in the liquid state when applying, a phosphor(s) 10 which exhibits good solubility and/or good suspensibility is desirable.

Inventors provided an agriculture composition comprising at least one phosphor which has a peak emission light wavelength in the range of 430 ^ 5 - 500 nm and/or 600 - 730 nm. As one embodiment, the agriculture

composition further comprising at least one solvent which comprises at least one selected from the group of water and organic solvent.

As one embodiment, the phosphor in the agriculture composition is at

20

least one selected from the group consisting of an inorganic phosphor or an organic phosphor.

As one preferred embodiment, the phosphor is at least one metal oxide 25 phosphor represented by following formula (I).

C1 pC2 q C3rC4sOt:MC - (I)

C1 is a monovalent cation which is at least one selected from the group consisting of Li, Na, K, Rb and Cs,

u

C2 is a divalent cation which is at least one selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn,

C3 is a trivalent cation which is at least one selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, Sm, Al, Ga, and In,

5 C4 is a tetravalent cation which is at least one selected from the group consisting of Si, Ti, and Ge, MC is a metal cation which is at least one selected from the group consisting of Cr 3+ , Eu 2+ , Mn 2+ , Mn 4+ , Fe 3+ , and Ce 3+ , and

p, q, r, s and t are integers on or more than 0, satisfying that

(1 p+2q+3r+4s)=2t, and at least one of p, q, r and s is on or more than 1 .

As one embodiment, inventors found a method for manufacturing the agriculture composition comprising adding at least one phosphor into a base composition. A preferable embodiment of a base composition is a pesticide formulation and a fertilizer formulation. The agriculture composition is good for implementation by applying to the surface of a plant leaves. With this agriculture composition, plant can be produced and/or enhanced its photosynthesis.

In another aspect, inventors provided a use at least one phosphor for agriculture with applying the phosphor(s) to the surface of a plant leaves. The above agriculture purpose is preferably producing a plant, and/or enhancing a photosynthesis of a plant. Later described phosphors can be used for this use. Agriculture compositions described below are other preferable embodiments when the phosphors applied onto the plant leaves in said use.

Description of drawings

Fig. 1 : shows black sheets covering a hydroponics system to cut natural light reaching to the system.

Fig. 2: shows a photo of Gaillardia plants of working example 5.

Fig. 3: shows the excitation and emission spectra of a phosphor synthesized as synthesis example 4.

Fig. 4: shows the excitation and emission spectra of a phosphor synthesized as synthesis example 5.

Fig. 5: shows the excitation and emission spectra of a phosphor synthesized as synthesis example 6.

Fig. 6: shows length and width of Komatsuna leaves. Fig. 7: shows shell weights of Edamame.

Fig. 8: shows durations until flowering of Arabidopsis thaliana.

Fig. 9: shows leaves numbers of Arabidopsis thaliana.

Fig. 10: shows weights of Arabidopsis thaliana.

List of reference signs in figure 1

100. a hydroponics system UH-CB01 G1 (UING Corp.)

1 10. a plant (Lettuce)

120. a black sheet

130. an illuminometer

Definitions

The above outlines and the following details are for describing the present invention, and are not for limiting the claimed invention. Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for the purpose of this Application.

In this application, the use of the singular includes the plural, and the words "a", "an" and "the" mean "at least one", unless specifically stated otherwise. In this specification, when one concept component can be exhibited by plural species, and when its amount (e.g. mass %, mol %) is described, the amount means the total amount of them, unless specifically stated otherwise.

Furthermore, the use of the term "including", as well as other forms such as "includes" and "included", is not limiting. Also, terms such as "element" or "component" encompass both elements or components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the term "and/or" refers to any combination of the elements including using a single element. In the present specification, when the numerical range is shown using "to", "-" or the numerical range includes both numbers before and after the "to", "-" or and the unit is common for the both numbers, unless otherwise specified. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

As used herein, "C x-y ", "C x -C y " and "C x " designate the number of carbon atoms in a molecule. For example, Ci-6 alkyl chain refers to an alkyl chain having a chain of between 1 and 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl and hexyl).

0 The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and

5 treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. If one or more of the incorporated literature and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.

^ The term "fluorescent" is defined as the physical process of light emission by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore lower energy, than the absorbed radiation.

5 The term "inorganic" means any material not containing carbon atoms or any compound that containing carbon atoms ionically bound to other atoms such as carbon monoxide, carbon dioxide, carbonates, cyanides, cyanates, carbides, and thiocyanates.

Q The term "emission" means the emission of electromagnetic waves by electron transitions in atoms and molecules.

According to the present invention, the term peak wavelength means publicly recognized meaning, in this specification which can

5

comprises both the main peak of an emission/absorption (preferably emission) spectrum having maximum intensity/absorption and side peaks having smaller intensity/absorption than the main peak. Preferably, the term peak wavelength is related to a side peak. Preferably, the term peak wavelength is related to the main peak having maximum

intensity/absorption .

Detailed Description of the invention

According to the present invention, an agriculture composition comprising at least one phosphor which has a peak emission light wavelength in the range of 430 - 500 nm or 600 - 730 nm, is provided.

Phosphors

According to the present invention, any type of publicly known phosphors having a peak emission light wavelength in the range of 430 - 500 nm or 600 - 730 nm, for example as described in the second chapter of

Phosphor handbook (Yen, Shinoya, Yamamoto), can be used as desired. Those phosphors can be inorganic phosphors and/or organic phosphors.

As another embodiment, the phosphors are preferable for plant growth, which has an absorption peak wavelength in UV and/or green light (420, 560 nm), and an emission peak wavelength in near infrared ray region (650 - 730 nm, more preferably from 650 - 700 nm). The phosphors are preferable which have a narrow full width at half maximum (hereafter "FWHM") of the light emission.

Inorganic phosphors

Inorganic phosphors of this invention can be selected from the group consisting of sulfides, thiogallates, nitrides, oxy-nitrides, silicates, metal oxides, apatites, phosphates, selenides, borates, carbon materials, and a combination thereof. One preferred embodiment of the silicate is a fluorescent mica and/or a fluorescent pearl pigment. The inorganic phosphors can be at least one metal oxide phosphor represented by following formula (I).

C1 pC2 q C3rC4sOt:MC - (I)

5

C1 is a monovalent cation which is at least one selected from the group consisting of Li, Na, K, Rb and Cs. As one phosphor represented by formula (I), plural species of C1 can be selected. C1 selected from Li 0 and/or Na is preferable.

C2 is a divalent cation which is at least one selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn. As one phosphor represented by formula (I), plural species of C2 can be selected.

^ C2 selected from Mg, Zn, Ca, Sr, Ba, and/or Sn is preferable, selected from Mg, Zn, Ca, Sr, and/or Ba is more preferable.

C3 is a trivalent cation which is at least one selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, Sm, Al, Ga, and In. As one phosphor represented by formula (I), plural species of C3 can be selected.

20

C3 selected from Y, Gd, Al, and/or Ga is preferable, selected from Al is more preferable.

C4 is a tetravalent cation which is at least one selected from the group consisting of Si, Ti, and Ge. As one phosphor represented by formula (I),

25 plural species of C4 can be selected. C4 selected from Si, and/or Ti is preferable, selected from Ti is more preferable.

MC is a metal cation which is at least one selected from the group consisting of Cr 3+ , Eu 2+ , Mn 2+ , Mn 4+ , Fe 3+ , and Ce 3+ . As one phosphor

2Q represented by formula (I), plural species of MC can be selected. MC

selected from Cr 3+ , Eu 2+ , Mn 2+ and/or Mn 4+ is preferable. MC selected from Cr 3+ , "Eu 2+ , Mn 2+ ", Mn 2+ , and Mn 4+ is more preferable. In the case plural MC selected, selecting same valent number cations is one preferable embodiment.

35

p, q, r, s and t are integers on or more than 0, satisfying that

(1 p+2q+3r+4s) =2t. At least one of p, q, r and s is on or more than 1 . It is one preferable embodiment that p, q, r, and s are each independently 0 - 6, more preferably 0 - 5, further preferably 0 - 3, furthermore preferably 0 - 2. It is preferable embodiment that t is 1 - 20, more preferably 1 - 9, further preferably 2 - 8, furthermore preferably 2 - 5. MC can be replaced with same valent number cation. In the case MC is Eu 2+ and/or Mn 2+ , q is on or more than 1 is preferable. In the case MC is Cr 3+ Fe 3+ and/or Ce 3+ , r is on or more than 1 is preferable. In the case MC is Mn 4+ , s is on or more than 1 is preferable.

As further preferred embodiment, the inorganic phosphor can be a Cr activated metal oxide phosphor, and/or a Mn activated metal oxide phosphor.

One embodiment of the Cr activated metal oxide phosphor is represented by following formula (II).

AxB y O z :Cr 3+ - (II)

A is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm. Preferably A is selected from Y and Gd.

B is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, and In. Preferably B is selected from Al and Ga.

x and y are integers. x≥0, y≥ 1 , and 1 .5(x+y) = z. Preferably x is 0 - 5, and y is 1 - 8. More preferably x is 0 - 3, and y is 1 - 5. Another embodiment of the Cr activated metal oxide phosphor is represented by following formula (III).

XaZbO c :Cr 3+ - (III) X is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn. Preferably X is selected from Mg, Co, and Mn.

Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In. Preferably Z is selected from Al and Ga.

a and b are integers. b≥0, a≥1 , and (a+1 .5b) = c. Preferably a is 1 - 3, and b is 0 - 6. More preferably a is 1 - 2, and b is 0 - 4.

One embodiment of the Mn activated metal oxide phosphor is represented by following formula (IV).

C2qC3rC4sO t :MC 2+ - (IV)

MC 2+ is a divalent metal cation selected from "Eu 2+ ", "Mn 2+ ", or "Eu 2+ , Mn 2+ ". Preferably MC 2+ is selected from "Mn 2+ ", or "Eu 2+ ,Mn 2+ ".

Definitions of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I). Embodiments of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I). As to a phosphor represented by formula (IV), it is preferable that q=1 - 5, r=0 - 4, s=0 - 3, and t=3 - 9, and more preferable that q=1 - 4, r=0 - 3, s=0 - 2, and t=4 - 8.

Another embodiment of the Mn activated metal oxide phosphor is represented by following formula (V).

Definitions of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I). Embodiments of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I). As to a phosphor represented by formula (V), it is preferable that q=0 - 9, r=0 - 15, s=0 - 8, and t=3 - 20, and more preferable that q=1 - 7, r=0 - 12, s=0 - 6, and t=4 - 19.

As a preferred embodiment of the present invention, the inorganic

5

phosphor can be selected from the group consisting of Al2O3:Cr 3+ , Y 3 AI 5 Oi 2 :Cr 3+ , MgO:Cr 3+ , ZnGa 2 O 4 :Cr 3+ , MgAI 2 O 4 :Cr 3+ , Sr 3 MgSi 2 O8:Mn 4+ , Sr 2 MgSi 2 O 7 :Mn 4+ , SrMgSi 2 O 6 :Mn 4+ , Mg 2 SiO :Mn 2+ , BaMg 6 Ti 6 Oi9:Mn 4+ , Mg 2 TiO 4 :Mn 4+ , Li 2 TiO 3 :Mn 4+ , CaAli 2 Oi 9 :Mn 4+ , ZnAI 2 O 4 :Mn 2+ , LiAIO 2 :Fe 3+ ,

10 LiAI 5 O 8 :Fe 3+ , NaAISiO 4 :Fe 3+ , MgO:Fe 3+ , Gd 3 Ga 5 Oi 2 :Cr 3+ ,

Gd 3 Ga 5 Oi 2 :Cr 3+ ,Ce 3+ , (Ca,Ba,Sr)MgSi 2 O 6 :Eu 2+ ,Mn 2+ ,

(Ca,Ba,Sr) 2 MgSi 2 O 7 :Eu 2+ ,Mn 2+ , (Ca,Ba,Sr) 3 MgSi 2 O 8 :Eu 2+ ,Mn 2+ , ZnS, InP/ZnS, CulnS 2 , CulnSe 2 , CulnS 2 /ZnS, carbon quantum dot, and

^ combination thereof.

For example, ": Eu 2+ , Mn 2+ " in one embodiment "MgSr 3 Si 2 O8:Eu 2+ , Mn 2+" means both Eu 2+ and Mn 2+ works as co-activations of a metal oxide phosphor of the invention. "(Ca, Ba, Sr)" in one embodiment "(Ca, Ba, Sr)

20

MgSi2O6:Eu2 + , Mn 2+ " means that Ca, Ba and Sr can be replaced each other to work as this phosphor.

A quantum dot material can be used as an inorganic phosphor. Preferable 25 embodiments of it is ZnS, InP/ZnS, CulnS 2 , CulnSe 2 , CulnS 2 /ZnS and/or carbon quantum dot. One preferred embodiment of this carbon quantum dot is a graphene quantum dot.

2Q More preferred embodiments of present inorganic phosphor can be

selected from the group consisting of AI 2 O 3 :Cr 3+ , Y 3 AI 5 Oi 2 :Cr 3+ , MgO:Cr 3+ , ZnGa 2 O 4 :Cr 3+ , MgAI 2 O 4 :Cr 3+ , Mg 2 TiO 4 :Mn 4+ , Li 2 TiO 3 :Mn 4+ , CaAli 2 Oi 9 :Mn 4+ and combination thereof. Those metal oxides can function as

micronutrients and/or fertilizer.

35

Organic phosphor Organic phosphors of this invention can be selected from the group consisting of fluorescein derivative, rhodamine derivative, coumarin derivative, pyrene derivative, cyanine derivative, perylene derivative, and di-cyano-methylene derivative, and combination thereof. Organic compounds which exhibit photo-luminesce can be used for this the purpose of the invention. For example, in the OLED field such compound is known as an emitter or a dopant. A fluorescent emitter in OLED can be more preferable for the invention.

Agriculture composition

Our invention provides an agriculture composition comprising the phosphor. In this invention and specification, an intermediate and an intermediate state (e.g. an intermediate of a polymer sheet, the polymer sheet is a final product) are excluded from the meaning of the agriculture composition. For applying to the leave surface, it is one preferable embodiment that the agriculture composition comprises less solidifying component (e.g. polymer, resin and/or crosslinking agent). As one embodiment, the mass ratio of the solidifying component to the total mass of the agriculture composition is 0 - 0.5 mass %, preferably 0 - 0.1 mass %, and more preferably 0 - 0.01 mass %. An agriculture composition comprises no solidifying component (0 mass %) is one preferable embodiment.

Here, above polymer and resin can has a weight average molecular weight in the range 5,000 - 50,000, more specifically 10,000 - 30,000. The molecular weight M w of polymer and resin can be determined by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.

Additive The agriculture composition can further comprise additives. Comprising a spreading agent and/or a surface treatment agent is one preferable embodiment.

When the agriculture composition applied onto the leaves, the agriculture composition had better to remain on the leaves for some period to exhibit its property. But wax secreted by leaves can inhibit this agriculture composition remained on leaves, and drop off it from the leaves. A spreading agent functions improving spreading performances, wettability, and/or adhesion of the agriculture composition. A surface treatment agent can change the polarity of the phosphor or leave surface (preferably the phosphor) to decrease repulsive force between them. Preferably a spreading agent can be selected from the group consisting of isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated C12- 18 fatty alcohols, oleic acid, oleyl ester, ethyl oleate, triglycerides, silicone oils, dipropylene glycol methyl ether, and combination thereof. One preferred embodiment of a spreading agent is Approach Bl (Trade mark, Kao Corp.).

As one embodiment, the mass ratio of the spreading agent to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 100 mass %, more preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %. As one embodiment, the mass ratio of the surface treatment agent to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 100 mass %, more preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.

The agriculture composition can further comprise an adjuvant, a dispersant, a surfactant, a fungicide, a pesticide, a fertilizer, an

antimicrobial agent, and/or an antifungal agent. An adjuvant can enhance permeability of effective component (e.g. insecticide), inhibit precipitation of solute in the composition, or decrease a phytotoxicity. The solutes (e.g. the phosphors) in the agriculture composition is not necessarily dissolved in the composition. In the case the agriculture composition is liquid, a dispersant is useful because it helps the solutes to be applied uniformly to the plant leaves. In here, a surfactant means it does not comprise or is not comprised by other additives, for example a spreading agent, a surface treatment agent and an adjuvant. In the case the agriculture composition is liquid, a phosphor with good suspensibility is desirable because the phosphor is easily suspended in the agriculture composition.

Preferably an adjuvant can be selected from the group consisting of a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives, and combination thereof.

Preferred embodiments of the surfactant are polyoxyethylene alkyl ethers (e.g., polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether); polyoxyethylene fatty acid diethers;

polyoxyethylene fatty acid monoethers; polyoxyethylene-polyoxypropylene block polymer; acetylene alcohol; acetylene glycol derivatives (e.g., acetylene glycol, polyethoxyate of acetylene alcohol, and polyethoxyate of acetylene glycol); silicon-containing surfactants (e.g., Fluorad (Trademark, Sumitomo 3M Ltd), MEGAFAC (Trademark, DIC Corp.), and Surufuron (Trademark, Asahi Glass Co., Ltd.)); and organic siloxane surfactants, such as, KP341 (Trademark, Shin-Etsu Chemical Co., Ltd.).

Examples of the above acetylene glycols include: 3-methyl-1 -butyne-3-ol, 3-methyl-1 -pentyne-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9- tetramethyl- 5-decyne-4,7-diol, 3,5-dimethyl-1 -hexyne-3-ol, 2,5-dimethyl-3- hexyne-2,5-diol, and 2,5-dimethyl-2,5- hexanediol.

Examples of anionic surfactants include: ammonium salts and organic amine salts of alkyldiphenylether disulfonic acids, ammonium salts and organic amine salts of alkyldiphenylether sulfonic acids, ammonium salts and organic amine salts of alkylbenzenesulfonic acids, ammonium salts and organic amine salts of polyoxyethylenealkylether sulfuric acids, and ammonium salts and organic amine salts of alkyl-sulfuric acids.

Further, examples of the amphoteric surfactants include 2-alkyl-N- carboxymethyl-N-hydroxyethyl imidazolium betaine, and laurylic acid amidopropyl hydroxy sulfone betaine.

Explanations of a pesticide and a fertilizer are described in later. Here, an active ingredient of pesticide formulation is a pesticide ingredient. And here, an active ingredient of fertilizer formulation is a fertilizer ingredient.

As one embodiment, the mass ratio of each 1 additive of dispersant, surfactant, fungicide, a pesticide, a fertilizer, antimicrobial agent and antifungal agent, to the mass of the phosphor in the agriculture

composition is 5 - 200 mass %, preferably 5 - 200 mass %, more preferably 5 - 150 mass %, further preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %. As one preferred embodiment, the mass ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 200 mass %, more preferably 5 - 150 mass %, further preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.

Solvent

The agriculture composition can further comprise at least one solvent which comprises at least one selected from the group of water and organic solvent. Known usual water can be used as said water, which can be selected from agricultural water, tap-water, industrial water, pure water, distilled water and deionized water. Including said organic solvent in the agriculture composition is useful for dissolving the solute. The organic solvent is preferably selected from alcohol solvent, ether solvent and mixture thereof. One preferable embodiment of said alcohol solvent is selected from ethanol, isopropanol, cyclohexanol, phenoxyethanol, benzyl alcohol or mixture thereof. More preferable embodiment of said alcohol solvent is ethanol. One preferable embodiment of said ether solvent is selected from dimethyl ether, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether or mixture thereof. More preferable embodiment of said ether solvent is dimethyl ether.

The mass ratio of said solvent(s) in the agriculture composition, to the total mass of the agriculture composition is preferably 70 - 99.95 mass %, more preferably 80 - 99.90 mass %, further preferably 90 - 99.90 mass %, furthermore preferably 95 - 99.50 mass %. One embodiment of the mass ratio of said water to the sum of other solvents is preferably 80 - 100 mass %, more preferably 90 - 100 mass %, further preferably 95 - 100 mass %, furthermore preferably 99 - 100 mass %. The said solvent is preferably water, ethanol, dimethyl ether or mixture thereof. The solvent consisting of water is one preferred embodiment to avoid unnecessary effect for animals.

The mass ratio of the phosphor(s) to the total mass of the agriculture composition is preferably 0.05 - 30 mass %, more preferably 0.1 - 10 mass %, further preferably 0.5 - 5 mass %, furthermore preferably 0.8 - 3 mass %. In the case the agriculture composition is liquid, the applied amount of the phosphor(s) on leaves depends on the phosphor's concentration and the agriculture composition's dose to be applied. The skilled person can control them based on an applied measure, a purpose, plant species, and so on. Of course, the sum of the mass ratio of said solvent and the mass ratio of the phosphor(s) to the total mass of the agriculture composition doesn't exceed 100 mass %.

The mol/L of the phosphor(s) in the agriculture composition is preferably 10 "7 - 10 "2 mol/L, more preferably 10 "6 - 10 "3 mol/L, further preferably 10 "5 - 10 "4 mol/L. In the case the phosphor has variety range of its molecular weight, known methods to get an average molecular weight (preferably a weight average molecular weight) can be used to calculate its mol/L (molar concentration).

Base composition

Inventors found a method for manufacturing an agriculture composition comprising adding at least one phosphor into a base composition. The base composition comprises at least one solvent. The definitions and embodiments of the phosphor and the solvent of this manufacturing method are independently same to described above. Before adding to the base composition, the phosphor can be solid state, and can be dissolved or dispensed in solvent. Some phosphors are good at dissolved by organic solvent. For avoiding evaporated or remained organic solvent affect the plant, soil or animals (including human), the skilled person can decrease the organic solvent concentration in the agriculture composition by diluting in the base composition. One preferable embodiment of the mass ratio of water to the total mass of the base composition is preferably 80 - 100 mass %, more preferably 90 - 100 mass %, further preferably 95 - 100 mass %, furthermore preferably 99 - 100 mass %.

The base composition can be at least one selected from the group consisting of a pesticide formulation and a fertilizer formulation. One embodiment of the manufacturing method is adding phosphor into the pesticide formulation to make an agriculture composition before applying it to plant.

Pesticide formulation can be at least one selected from the group consisting of an herbicide, insecticide, insect growth regulator, nematicide, termiticide, molluscicide, piscicide, avicide, rodenticide, predacide, bactericide, insect repellent, animal repellent, antimicrobial, fungicide, disinfectant, and sanitizer formulation. Known fertilizer formulation can be used for this manufacturing method. A fertilizer (fertiliser) ingredient can be natural or synthetic material. Components of the phosphor can function as fertilizer by themselves, and can be absorbed by plant root when swept away from the leave surface.

Applying the agriculture composition to the surface of a plant leaves This invention provides a method comprising applying the agriculture composition to the surface of a plant leaves. This applying method can set the phosphor on the leaves, which has a peak emission light wavelength 0 in the range of 430 - 500 nm or 600 - 730 nm. If the method applies

agriculture composition on leaves intentionally, incidental applying to another portion (e.g. stem) is acceptable.

5 This invention provides a method producing a plant(s) with applying the agriculture composition to the surface of a plant leaves. And this invention provides a method enhancing a photosynthesis a plant(s) with applying the agriculture composition to the surface of a plant leaves.

^ In the case the agriculture composition doesn't comprises any solvent, the agriculture composition can be applied to the surface of the plant leaves by powdering, loading or combination thereof, preferably by powdering. An applied amount of the agriculture composition as average can be

5 0.000001 - 0.001 g/cm 2 , preferably 0.00001 - 0.0001 g/cm 2 , and more

preferably 0.00003 - 0.00008g/cm 2 .

The leaves area of 1 plant can be measured by known method and Q device. A leaf area meter can be used to measure it. One embodiment is a LI3000C Area Meter (Li-COR Corp.). The leaves area can be measured by separating all leaves from 1 plant body, getting a photo image or scan each 1 leaf, and processing these images.

In the case the agriculture composition comprises a solvent(s), the agriculture composition can be applied to the surface of the plant leaves by spraying, watering, dropping, dipping, coating or combination of thereof, preferably by spraying. One embodiment of said coating is brush coating. An average amount of the agriculture composition to be applied to the surface of the plant leaves can be 0.0005 - 0.1 mL/cm 2 of the surface,

5

preferably 0.001 - 0.01 mL/cm 2 of the surface.

The agriculture composition can be applied one or more times during the growing season of the plant. Growing season can be a period from the first

10 leaf develop until the whole flesh weight of a plant become plateaued. The total timing of the agriculture composition to be applied can be controlled by applied amount and/or additive(s). A spreading agent can help the phosphor remain on the leaves. The timing can be 1 - 10 times/1 plant

^ generation, preferably 1 - 5 times/1 plant generation, more preferably 1 - 4 times/1 plant generation.

The plant can be flowers, vegetables, fruits, grasses, trees and

horticultural crops. One embodiment of the plant can be Gaillardia,

20

Lettuce, Rucola, Komatsuna (Japanese mustard spinach), Radish

(preferably Gaillardia, Lettuce, or Rucola), Campanularapunculus,

Rudbeckia, Edamame (Glycine max), or Arabidopsis thaliana (preferably Gaillardia, Lettuce, Rucola, Komatsuna or Radish, more preferably

25 Gaillardia, Lettuce, or Rucola).

The environment of growing plant can be natural environment, a green house, a plant factory and indoor cultivation, preferably natural

2Q environment and a green house. One embodiment of the natural

environment is an outside farm.

The synthesis examples and working examples below provide descriptions of the present inventions but not intended to limit scopes of the inventions.

35 Working Examples

Synthesis Example 1 : Synthesis of AhC^Cr 3

The precursors of Al2O3:Cr 3+ phosphor is synthesized by a co-precipitation method. The raw materials of Aluminium Nitrate Nonahydrate and

Chromium(lll) nitrate nonahydrate are dissolved in deionized water with a stoichiometric molar ratio of 0.99:0.01 . NH 4 HCO3 is added to the mixed chloride solution as a precipitant, and the mixture is stirred at 60 °C for 2h. The resultant solution is dried at 95 °C for 12 h, then the preparation of the precursors is completed. The obtained precursors are oxidized by calcination at 1300 °C for 3 h in air. To confirm the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC). Photoluminescence (PL) spectra are measured using a Spectra fluorometer (JASCO FP-6500) at room temperature.

The absorption peak wavelengths of Al2O3:Cr 3+ are 410 - 430 nm and 550 - 570 nm, the emission peak wavelength is in the range from 680 - 700 nm, the full width at half maximum (hereafter "FWHM") of the light emission from Al2O3:Cr 3+ is on or less than 30 nm.

Working Example 1 : Composition 1

10mL of a spreading agent (Approach Bl, Trade mark, Kao Corp.) is added in 10L of water, and stirred. Al2O3:Cr 3+ phosphor of Synthesis example 1 is added to the resultant solution to be 1 .0 % mass

concentration (1 .0 mass %).

Working Example 2: Plant growth test 1

Hydroponics systems UH-CB01 G1 (UING Corp.) are prepared with a white LED light sources at the top of the systems. The systems are set inside of a room.

Light conditions are below. Photosynthetic Photon Flux Density (PPFD) are 200 mol-m _2 -s _1 . Puts the light on at 6:00am, puts the light off at 22:00 (light on 16 h/day). Black sheets are set to cover the system for cutting natural light reach plants as like shown in Fig 1 . The sheets are shut unless necessity e.g. watering, evaluation.

During this test, sufficient water is maintained under plants to cover their roots. The temperature is controlled at room temperature, approximately 25 °C.

4 seedlings of Lettuce are planted on this system as working example group 1 . As comparative example group 1 , 4 seedlings are planted on this system.

Composition 1 is sprayed on the working example group 1 approximately uniformly by 10 times spraying at 1 st day, 8 th day and 16 th day from planting date. The 10 times spraying volume is approximately 8 mL.

Leaves weights at 23 rd days from planting date are evaluated as below. All leaves of 1 plant are separated. Other parts of plant (e.g. stem, root) are not used for this evaluation. Soon, fresh leaves weight of 1 plant is weighted. Leaves are dried in a desiccator at 85 °C for more than 24 h. Then dried leaves weight of 1 plant is weighted. Average of 4 plants in working example group 1 is described in below Table 1 . Same procedures are done to evaluate the comparative example group 1 .

Table 1

This test shows that the working example plants grow more than the comparative example ones. Working Example 3 and 4: Composition 2 and 3

Composition 2 and 3 are prepared same to the working example 1 with changing Al2O3:Cr 3+ phosphor concentration as 0.25 mass % and 0.50 mass %.

Working Example 5: Plant growth test 2

Below experiments are conducted in a greenhouse under natural light (sun light). The greenhouse is located at Tottori prefecture, Japan. The starting date is in April.

8 seedlings (38 days after seeded) of Gaillardia are planted in soil. Later, normal watering is conducted 1 time/ 1 day on all seedlings and soil by a watering can.

10 days after planting, the composition 1 (working example 1 , 1.0 mass %) is sprayed on 2 seedlings by 4 times spraying. The 4 times spraying volume is approximately 4 mL.

Same procedures are taken with the composition 2 (working example 3, 0.25 mass %) sprayed on 2 seedlings. Same procedures are taken with the composition 3 (working example 4, 0.50 mass %) sprayed on 2 seedlings.

Fig 2 shows those plants 57 days after planting. This test shows that the working example plants grow more than the comparative example ones. 1.0 mass % sprayed group bloomed at 57 days after planting. The growth is accelerated by a dense concentration composition. And a concentration dependency is observed in this test.

Synthesis Example 2: Synthesis of Mg 2 Ti0 4 :Mn 4+

The precursors of Mg2TiO 4 :Mn 4+ phosphor is synthesized by a solid-state reaction. The raw materials of Magnesium oxide, Titanium oxide and Manganese oxide are prepared with a stoichiometric molar ratio of

2.000:0.999:0.001. These chemicals are put in a mortar and mixed by a pestle for 30 minutes. The resultant is oxidized by calcination at 1000 °C for 3 h in air. To confirm the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC). Photoluminescence (PL) spectra are measured using a Spectro fluorometer (JASCO FP-6500) at room temperature.

The absorption peak wavelengths of Mg2TiO 4 :Mn 4+ are 300 - 340 nm and 460 - 520 nm, the emission peak wavelength is in the range from 650 - 670 nm, the FWHM of the light emission from Mg2TiO 4 :Mn 4+ is on or less than 60 nm.

Working Example 6: Composition 4

Composition 4 is prepared same to the working example 1 with changing from Al2O3:Cr 3+ (synthesis example 1 ) to Mg2TiO 4 :Mn 4+ (synthesis example 2).

Working Example 7: Plant growth test 3

Same tests are done same to the working example group 2 with changing from the composition 1 to the composition 4.

Without using composition 1 to 4, Comparative example group 2 are grown in parallel.

Leaves weights at 23 rd days from planting date are evaluated as same procedures described in above working example 2. The results are shown in below Table 2.

Table 2

Working example Comparative group 2 example group 2

Fresh leaves weight (g) 46.4 42.04

Dried leaves weight (g) 2.04 1.75 This test shows that the working example plants grow more than the comparative example ones.

Working Example 8: Plant growth test 4

Below experiments are conducted in a greenhouse under natural light (sun light). 12 Komatsuna (Japanese mustard spinach) seedlings are planted in soil. 6 seedlings are working example group 3 (composition 4 spraying) and other 6 seedlings are comparative example group 3 (water spraying). 1 day after planting, the composition 4 is sprayed on working example group 3 (6 seedlings) by 10 times spraying. The 10 times spraying volume is approximately 8 ml_. 1 day after planting, water is sprayed on

comparative example group 3 (6 seedlings) by 10 times spraying. The 10 times spraying volume is approximately 8 ml_.

Same procedures are taken on 8 th , 16 th , 21 st and 28 th days after planting date.

Leaves weights at 35 th days from planting date are evaluated as same procedures described in above working example 2. The results are shown in below Table 3.

Table 3

This test shows that the working example plants grow more than the comparative example ones.

Synthesis Example 3: Synthesis of Y 2 MgTiOe:Mn +

The phosphors precursors are synthesized by a conventional polymerized complex method. The raw materials of yttrium oxide, magnesium oxide, titanium oxide and manganese oxide are prepared with a stoichiometric molar ratio of 2.000:1 .000: 0.999:0.001 . These chemicals are put in a mortar and mixed by a pestle for 30 minutes. The resultant materials are oxidized by firing at 1500 °C for 6 h in air.

To confirm the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).

Photoluminescence (PL) spectra are measured using a Spectra

fluorometer (JASCO FP-6500) at room temperature.

The absorption peak wavelengths of Y2MgTiO6:Mn 4+ are 300 - 340 nm and 320 - 490 nm, the emission peak wavelength is in the range from 700 nm.

Working Example 9: Composition 5

Composition 5 is prepared same to the working example 1 with changing from Al2O3:Cr 3+ (synthesis example 1 ) to Y2MgTiO6:Mn 4+ (synthesis example 3).

Working Example 10: Plant growth test 5

Below experiments are conducted in a greenhouse under natural light (sun light). 12 Radish seedlings are planted in soil. 6 seedlings are working example group 4 (composition 5 spraying) and other 6 seedlings are comparative example group 4 (water spraying).

1 day after planting, the composition 4 is sprayed on working example group 3 (6 seedlings) by 10 times spraying. The 10 times spraying volume is approximately 8 ml_. 1 day after planting, water is sprayed on

comparative example group 3 (6 seedlings) by 10 times spraying. The 10 times spraying volume is approximately 8 ml_.

Same procedures are taken on 8 th and 16 th days after planting date.

Roots weights at 23 rd days from planting date are evaluated as same procedures described in above working example 2. In this example, not leaves but roots are treated and evaluated. The results are shown in below Table 4. Table 4

5

This test shows that the working example plants grow more than the comparative example ones.

10

Synthesis Example 4: Synthesis of Ba2YTaOe:Mn +

The present example refers to the synthesis of the phosphor Ba2YTaO6:Mn 4+ with a Mn concentration of 1 mol%. The phosphor is

15 prepared according to conventional solid-state reaction methods, using Ba2CO3, Y2O3, Ta2O5 and MnO2 as starting materials. These chemicals are mixed according to their stoichiometric ratio and mixed with acetone in an agate mortar. The powder thus obtained is pelletized at 10 MPa, placed into

2Q an alumina container and heated at 1400 °C for 6 h in the presence of air.

After cooling the residue is well grinded for characterization. For confirmation of the structure, XRD measurements are performed using an X-ray diffractometer. Photoluminescence (PL) spectra is taken using a Spectro fluorometer at room temperature. The XRD patterns proofs that the

?

main phase of the product consisted of Ba2YTaO6. The photoluminescence excitation spectrum shows a UV region from 300 - 400 nm while the emission spectrum exhibits a deep red region from 630 - 710 nm. Excitation and emission spectra are provided in Figure 3.

30 The absorption peak wavelengths of Ba2YTaO6:Mn 4+ is 310 - 340 nm, and the emission peak wavelength is in the range from 680 - 700 nm.

Synthesis Example 5: Synthesis of NaLaMqWQ 6 :Mn

The present example refers to the synthesis of the phosphor

35

NaLaMgWO6:Mn 4+ with a Mn concentration of 1 mol%. The phosphor is prepared according to conventional solid-state reaction methods, using Na2CO3, La2O3, MgO, WO3 and MnO2 as starting materials. La2O3 is preheated at 1200 °C for 10 h in the presence of air. The chemicals are mixed according to their stoichiometric ratio and mixed with acetone in an

5

agate mortar. The powder thus obtained is pelletized at 10 MPa, placed into an alumina container and heated at 1300 °C for 6 h in the presence of air. After cooling the residue is well grinded for characterization. For confirmation of the structure, XRD measurements are performed using an

10 X-ray diffractometer. Photoluminescence (PL) spectra are taken using a Spectro fluorometer at room temperature. The XRD patterns proofs that the main phase of the product consisted of NaLaMgWO6. The photoluminescence excitation spectrum shows a UV region from 300 - 400

^ 5 nm while the emission spectrum exhibited a deep red region from 660 - 750 nm. Excitation and emission spectra are provided in Figure 4.

The absorption peak wavelengths of NaLaMgWO6:Mn 4+ is 310 - 330 nm, and the emission peak wavelength is in the range from 690 - 720 nm.

20

Working Example 11 : Plant growth test 6

In order to evaluate the effect of the phosphors on plant growth tests using hydroponic plant systems are conducted. Two aqueous solutions are prepared, one comprising 1 wt.% NaLaMgWO6:Mn 4+ phosphor (Synthesis

25 Example 5) and the other free of the phosphor. The tests are performed with hydroponic system of UING Corp. using a white LED on top of the boxes comprising young lettuce and rucola plants and enough water. The solutions are sprayed on the first day of the test series and on day 8. After day 16 the

2Q plants treated with the phosphor solution shows 10 % increase in height versus the comparison.

Synthesis Example 6: Synthesis of Si 5 PeQ25:Mn +

The present example refers to the preparation of the phosphor Si5P6O25:Mn 4+ with an Mn concentration of 0.5 mol%. The phosphor is prepared according to conventional solid-state reaction methods, using S1O2, NH 4 H2PO 4 and MnO2 as starting materials. The chemicals are mixed according to their stoichiometric ratio and mixed with acetone in an agate mortar. The powder thus obtained is pelletized at 10 MPa, placed into an alumina container, pre-heated 300 °C for 6 h. The pre-heated powder is grinded, pelletized at 10 MPa, placed again in an alumina container and heated at 1000 °C for another 12 hours in the presence of air. After cooling the residue is well grinded for characterization. For confirmation of the structure, XRD measurements are performed using an X-ray diffractometer. Photoluminescence (PL) spectra are taken using a Spectra fluorometer at room temperature. The XRD patterns proofs that the main phase of the product consisted of S15P6O25. The photoluminescence excitation spectrum shows a UV region from 300 nm to 400 nm while the emission spectrum exhibited a deep red region in the range from 670 - 690 nm. Excitation and emission spectra are provided in Figure 5.

Working Example 12: Plant growth test 7

In order to evaluate the effect of the phosphors on plant growth tests using hydroponic plant systems are conducted. Two aqueous solutions are prepared, one comprising 1 wt.% Si5P6O25:Mn 4+ phosphor (Synthesis Example 6) and the other free of the phosphor. The tests are performed with hydroponic system of UING Corp. using a white LED on top of the boxes comprising young lettuce and rucola plants and enough water. The solutions are sprayed on the first day of the test series and on day 8. After day 16 the plants treated with the phosphor solution shows 10 % increase in height versus the comparison.

Synthesis Example 7: Synthesis of CaMgSi 2 06:Eu 2+ , Mn2 +

The phosphor precursors of CaMgSi2O6:Eu 2+ , Mn2 + are synthesized by a conventional co-precipitation method.

CaCI 2 · 2H 2 O (0.0200 mol, Merck), SiO 2 (0.05 mol, Merck), EuCIs · 6H 2 O

(0.0050 mol, Auer-Remy), MnCI 2 · 4H 2 O (0.0050 mol, Merck), and MgCI 2 4H2O (0.0200 mol, Merck) are dissolved in deionized water. NH 4 HCO3 (0.5 mol, Merck) is dissolved separately in deionized water.

The two aqueous solutions are simultaneously stirred into deionized water. The combined solution is heated to 90°C and evaporated to dryness.

Then, the residue is annealed at 1000°C for 4 hours under an oxidative atmosphere, and the resulting oxide material is annealed at 1000°C for 4 hours under a reductive atmosphere.

To confirm the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).

Photoluminescence (PL) spectra is measured using a Spectro fluorometer (JASCO FP-6500) at room temperature. The emission peak wavelengths of CaMgSi 2 O 6 :Eu 2+ , Mn2 + is 570 - 600 nm and 670 - 710 nm.

Working Example 13: Plant growth test 8

In order to evaluate the effect of the phosphors on plant growth, tests under natural light in green house are conducted. Four aqueous solutions are prepared, each three comprising 0.25 mass%, 0.50 mass%, 1 .00 mass% Al2O3:Cr 3+ phosphor (Synthesis Example 1 ) and the other free of the phosphor (Control, 0 mass %). 2 weeks after seeding, 4 seedlings of Campanularapunculus are planted in soil. 4 weeks after planting, each solutions are sprayed to the plants. 8 weeks after spraying, the height of each seedlings is evaluated. Versus the control (0 mass% treated plant), each plant treated with 0.25 mass %, 0.50 mass % and 1 .00 mass % shows 16 %, 24 % and 35 % increases in height.

Working Example 14: Plant growth test 9

In order to evaluate the effect of the phosphors on plant growth, tests under natural light in green house are conducted. Two aqueous solutions are prepared, one comprising 1 .00 mass% Al2O3:Cr 3+ phosphor (Synthesis Example 1 ) and the other free of the phosphor (Control, 0 mass %). 2 weeks after seeding, 2 seedlings of Rudbeckia Toto (trade mark) Gold are planted in soil. 4 weeks after planting, each solutions are sprayed to the plants. 8 weeks after spraying, the height of each seedlings is evaluated. Versus the control (0 mass% treated plant), the plants treated with 1 .00 mass % shows 29 % increases in height.

Working Example 15: Plant growth test 10

In order to evaluate the effect of the phosphors on plant growth, tests under natural light in green house are conducted. These tests are conducted from July in Kanagawa prefecture, Japan. 3 aqueous solutions are prepared, two each comprising 1 .00 mass% Al2O3:Cr 3+ phosphor (Synthesis Example 1 ) and 1 .00 mass% Y2MgTiO6:Mn 4+ phosphor (Synthesis Example 3), and the other free of the phosphor (Control, 0 mass %). 2 weeks after seeding, seedlings of Komatsuna (Japanese mustard spinach) are planted in soil, and are treated with each solution by spraying. 13 days after then, 2 nd spraying is conducted. 14 days after 2 nd spraying, 3 rd spraying is conducted. 7 days after 3 rd spraying (in September), leaves of Komatsuna are harvested.

Length and width of leaves are measured. Average of them are shown in below Figure 6.

Working Example 16: Plant growth test 11

In order to evaluate the effect of the phosphors on plant growth, tests under natural light in green house are conducted. These tests are conducted from July in Kanagawa prefecture, Japan. 2 aqueous solutions are prepared, one comprising 1 .00 mass% Mg2TiO 4 :Mn 4+ phosphor (Synthesis Example 2), and the other free of the phosphor (Control, 0 mass %). 20 days after seeding, seedlings of Edamame (Glycine max) are planted in soil, and are treated with each solution by spraying. 21 days after then, 2 nd spraying is conducted. 14 days after 2 nd spraying (in September), shells of Edamame are harvested. Fresh weight of shells is measured. Average of them are shown in below Figure 7.

Working Example 17: Plant growth test 12

In order to evaluate the effect of the phosphors on plant growth, tests under LED light in laboratory room are conducted. Light conditions are 8 hours LED white light PPFD:150, 16 hours dark in each day.

3 aqueous solutions are prepared, two each comprising 1 .00 mass% Al2O3:Cr 3+ phosphor (Synthesis Example 1 ) and Mg2 ~ nO 4 :Mn 4+ phosphor (Synthesis Example 2), and the other free of the phosphor (Control, 0 mass %).

2 weeks after seeding, seedlings of Arabidopsis thaliana are treated with phosphor solutions by spraying at the frequency of 1 time/ 1 week.

As shown in below Figure 8, phosphor treating change the growing duration (days) from seeding until flowering begins. At the timing of flowering begins, leaves number of each seedlings are counted as show in below Figure 9, and each seedling is harvested and fresh weight is measured as shown in below Figure 10. Each number are average ones of each group. Phosphor treating slightly increases the growing duration of Arabidopsis thaliana until flowering. And phosphor treating increases leaves numbers and fresh weight of Arabidopsis thaliana.

Synthesis Example 8: Synthesis of Cai4AlioZn 6 Q35:Mn 4+

The precursors of Cai 4 A oZn6O35:Mn 4+ are synthesized by a solid phase reaction. The raw materials of calcium oxide, aluminium oxide, zinc oxide and manganese oxide are prepared with a stoichiometric molar ratio of 14.000:9.850:6.000:0.015. The chemicals are put in a mortar and mixed by a pestle for 30 minutes. The resultant materials are oxidized by firing at 1200 °C for 6 h in air. To confirnn the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC). Photoluminescence (PL) spectra are measured using a Spectro fluorometer (JASCO FP-6500) at room temperature. The absorption peak wavelengths are in the range of 280 - 340 nm, and 430 - 480 nm. The emission peak wavelength is in the range from 690 - 740 nm.