KR20180095286A - Polymer, organic photodiode comprising the same and photoelectric plethysmography sensor - Google Patents

Abstract

The present invention relates to a polymer including a unit represented by chemical formula 1. The present invention further relates to an organic electronic device including the same. An organic photodiode comprising the polymer can be applied to a photoelectric pulse wave sensor along with a light source.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer, an organic photodiode including the same, and a photoelectric pulse wave sensor including the same. BACKGROUND ART < RTI ID = 0.0 >

TECHNICAL FIELD [0001] The present invention relates to a polymer, an organic photodiode including the same, and a photoelectric pulse-wave sensor including the same.

Photoelectricplethysmograph (PPG) sensor is a pulse wave measurement method that can detect heart rate activity by measuring blood flow through a blood vessel using the optical characteristics of a living tissue. Pulse is a pulsating wave of blood that the blood swells in the heart. It can be measured by changing the blood flow, which is caused by the relaxation and contraction of the heart, that is, the volume change of the blood vessel. The optical pulse measurement is a method of measuring pulse waves using light. The photodiode senses changes in optical characteristics such as reflection and absorption transmittance of living tissues when the volume is changed, thereby measuring pulses . This method is widely used because it has non-invasive pulse measurement capability, miniaturization and ease of use and is easy to develop a wearable life signal detection sensor. However, the optical pulse wave measurement sensor has a problem that the measurement signal is severely distorted when the motion is accompanied.

Therefore, it is necessary to develop a flexible, wearable PPG sensor to enhance the body adhesive force, and it is necessary to develop a high performance organic photodiode (OPD) and a light source (LED, OLED, etc.).

Nature communications, 5, 5745, 2014

The present invention provides a polymer, an organic photodiode including the same, and a photoelectric pulse wave sensor including the same.

According to one embodiment of the present invention, there is provided a polymer comprising a unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

n is an integer from 1 to 10,000,

R 1 to R 6 are the same or different from each other and each independently represents a linear or branched alkyl ester group; A substituted or unsubstituted straight or branched alkyl group; A substituted or unsubstituted straight or branched alkoxy group; Or a substituted or unsubstituted straight or branched thioalkoxy group.

According to an embodiment of the present invention, there is also provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes the above-mentioned polymer.

According to one embodiment of the present invention, there is provided a photoelectrochemical pulse wave sensor including the above-described organic photodiode.

According to one embodiment of the present invention, the unit represented by the formula (1) has a specific orientation of F of the two thienothiophene structures, so that the crystallinity of the polymer containing the two units can be improved.

In addition, various substituents may be introduced into R 1 to R 6 of the above formula (1) to easily control solubility and crystallinity.

Since the polymer comprising the unit represented by Formula 1 according to an embodiment of the present invention has the maximum absorption wavelength in the absorption wavelength region of hemoglobin, the organic photodiode including the polymer may be combined with a photoelectric pulse wave sensor Can be applied.

1 is a cross-sectional view illustrating an organic photodiode according to an embodiment of the present invention.
2 and 3 are graphs showing the UV-vis absorption spectrum of Polymer 1. Fig.
4 is a cyclic voltammetry graph of Polymer 1. Fig.
5 and 6 are graphs showing the UV-vis absorption spectrum of Polymer 1. Fig.
7 is a cyclic voltammetry graph of Polymer 2. Fig.
8 to 11 are graphs showing changes in voltage-current density according to the photoactive layer coating rmp of the organic photodiode according to Examples 1 to 4.
FIGS. 12 to 15 are graphs showing the response of the organic photodiodes of Examples 1 to 4 irradiated with a light source (600 nm, 12 mW / cm ² ).
FIGS. 16 to 19 are graphs of the organic light emitting diodes of Examples 1 to 4 irradiated with a light source (600 nm, 12 mW / cm ² ) and measured according to a voltage applied with a _dark current ratio against _light current (I _light / I _dark ).

Hereinafter, the present specification will be described in detail.

The present invention provides a polymer comprising the unit represented by the above formula (1).

According to one embodiment of the present invention, the unit represented by the formula (1) has a specific orientation of F of the two thienothiophene structures, so that the crystallinity of the polymer containing the two units can be improved. Accordingly, due to the constant orientation of F, the organic photodiode including the crystalline enhanced polymer as the photoactive layer increases the mobility of holes flowing through the polymer, and as a result, the photoelectric pulse wave sensor Can be improved.

In addition, the unit represented by the formula (1) has a structure in which the F of the two thienothiophene structures has a certain directionality, and the unit in which the F has a certain directionality has electron-negativity, The HOMO energy level is lowered, so that the oxidation stability is excellent. In addition, the organic photodiode in which the F includes a polymer including units having a certain directionality may have an improved dark current value.

In addition, when the unit having the constant directionality of F and the unit having no constant directionality of F are compared, it is possible to improve the crystallinity of the polymer containing the unit represented by the formula (1) Accordingly, the charge (hole) mobility can be increased.

As used herein, the term "unit" means a repeating structure contained in a monomer of a polymer, wherein the monomer is bonded to the polymer by polymerization.

In this specification, the meaning of "including a unit" means that it is included in the main chain in the polymer.

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

Examples of such substituents are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; An alkyl group; An alkenyl group; An alkoxy group; Thioalkoxy groups; Ester group; A carbonyl group; A carboxyl group; A hydroxy group; A cycloalkyl group; An aryloxy group; An alkyloxy group; An aryl group; And a heterocyclic group, or has no substituent group.

The substituents may be substituted or unsubstituted with an additional substituent.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen in the ester group by a straight-chain, branched or cyclic alkyl group of 1 to 25 carbon atoms or an aryl group of 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, N-octyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl and cyclooctyl Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy and p- But is not limited thereto.

In the present specification, the thioalkoxy group may be linear, branched or cyclic. The number of carbon atoms of the thioalkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, and styrenyl groups.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, a fluorenyl group is a structure in which two cyclic organic compounds are connected through one atom.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing at least one of O, N and S as a hetero atom. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heteroaryl group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, an isoxazolyl group, A benzothiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the above heteroaryl groups.

In the present specification, the aryl group in the aryloxy group and arylthioxy group is the same as the above-mentioned aryl group. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, Naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Phenanthryloxy, 9-phenanthryloxy and the like. Examples of the arylthioxy group include phenylthio group, 2-methylphenylthio group, 4-tert-butylphenyl And the like. Examples of the aryl sulfoxy group include a benzene sulfoxy group and a p-toluenesulfoxy group, but the present invention is not limited thereto.

In the present specification, the alkyl group in the alkylthio group is the same as the alkyl group described above. Specific examples of the alkyloxy group include methylthio group, ethylthio group, tert-butylthio group, hexylthio group, octylthio group and the like, but are not limited thereto.

According to one embodiment of the present invention, in the general formula (1), R 1 to R 6 are the same or different and are each independently a branched alkyl ester group; A branched alkyl group; Or a branched alkylthio group.

According to one embodiment of the present invention, in the general formula (1), R1 to R6 are the same or different from each other, and each independently represents a 2-ethylhexyl ester group; 2-ethylhexyl group; Or a 2-ethylhexylthio group.

According to one embodiment of the present invention, in the general formula (1), R1 to R6 are the same or different from each other, and each independently represents a 2-ethylhexyl ester group; 2-ethylhexyl group; Or a 2-ethylhexylthio group.

According to one embodiment of the present invention, in the general formula (1), R 1 and R 2 are branched chain alkyl ester groups.

According to one embodiment of the present invention, in the general formula (1), R 1 and R 2 are 2-ethylhexyl ester groups.

According to one embodiment of the present invention, in the general formula (1), R 3 and R 4 are branched alkyl groups.

According to one embodiment of the present invention, in the above formula (1), R 3 and R 4 are 2-ethylhexyl groups.

According to one embodiment of the present invention, in the general formula (1), R5 and R6 represent a branched chain alkyl group.

According to one embodiment of the present invention, in the above formula (1), R5 and R6 are 2-ethylhexyl groups.

According to one embodiment of the present invention, in the general formula (1), R 5 and R 6 are alkylthio groups of a branched chain.

According to one embodiment of the present invention, in the above formula (1), R5 and R6 are 2-ethylhexylthio groups.

According to one embodiment of the present disclosure, the end of the polymer is an aryl group substituted with a haloalkyl group.

According to one embodiment of the present disclosure, the terminal group of the polymer is an aryl group substituted with a trifluoromethyl group.

According to one embodiment of the present disclosure, the terminal group of the polymer is a phenyl group substituted with a trifluoromethyl group.

According to one embodiment of the present disclosure, the terminal group of the polymer is a 4- (trifluoromethyl) phenyl group.

As used herein, the term "terminal group" means a structure at both ends excluding a repeating unit in a polymer.

According to one embodiment of the present disclosure, the polymer is any one selected from the following structures.

and n is an integer of 1 to 10,000.

According to one embodiment of the present disclosure, the number average molecular weight of the polymer is preferably from 500 to 1,000,000. Preferably, the number average molecular weight of the polymer is 10,000 to 100,000. According to one embodiment of the present disclosure, the number average molecular weight of the polymer is from 30,000 to 100,000.

According to one embodiment of the present disclosure, the polymer may have a molecular weight distribution of from 1 to 100. Preferably, the polymer has a molecular weight distribution of from 1 to 3. The lower the molecular weight distribution and the higher the number average molecular weight, the better the electrical and mechanical properties.

In addition, the number-average molecular weight is preferably 100,000 or less in order to have a solubility of more than a certain level and to be advantageous in application of a solution coating method.

The polymer can be produced on the basis of the following production example.

According to one embodiment of the present disclosure, the polymer has a maximum absorption wavelength at 500 nm to 800 nm, preferably 550 nm to 750 nm, more preferably 600 nm to 750 nm.

The polymer containing the unit represented by the formula (1) according to one embodiment of the present invention has a maximum absorption wavelength in the above-described range, and therefore is similar to the absorption wavelength of hemoglobin having an absorption wavelength at a wavelength of 600 nm to 750 nm. Therefore, the organic photodiode including the polymer can be applied to the photoelectric pulse wave sensor.

In one embodiment of the present disclosure, the HOMO energy level of the polymer is from 5 eV to 5.9 eV.

In the present specification, the HOMO energy level is measured by cyclic voltammetry, which is an electrochemical method. The LUMO energy level is the energy band gap difference from the UV edge in the HOMO energy. .

Specifically, the cyclic voltammetry is composed of a working electrode which is a carbon electrode, a reference electrode, and a counter electrode which is a platinum plate. It is a method to measure current flowing. The calculation formulas of HOMO and LUMO are as follows.

[expression]

HOMO (or LUMO) (eV) = - 4.8- (E _onset- E _{1/2 (Ferrocene)} )

In one embodiment of the present disclosure, the polymer has a solubility in chlorobenzene of 0.1 wt% to 20 wt%. The solubility measurement may refer to a value measured at room temperature.

According to one embodiment of the present disclosure, there is provided a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes the polymer.

An organic photodiode according to an embodiment of the present invention includes a first electrode, a photoactive layer, and a second electrode. The organic photodiode may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

According to one embodiment of the present disclosure, the organic photodiode may further include an additional organic layer. The organic photodiode can reduce the number of organic layers by using organic materials having various functions at the same time.

According to one embodiment of the present disclosure, the first electrode is an anode and the second electrode is a cathode. In another embodiment, the first electrode is a cathode and the second electrode is an anode.

According to one embodiment of the present invention, the organic photodiodes may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode.

In another embodiment, the organic photodiodes may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

According to one embodiment of the present invention, the organic photodiode has a normal structure. In the normal structure, the substrate, the anode, the organic material layer including the photoactive layer, and the cathode may be stacked in this order. Also, a passivation layer may be further included on the cathode.

According to one embodiment of the present disclosure, the organic photodiode is an inverted structure. In the inverted structure, the substrate, the cathode, the organic material layer including the photoactive layer, and the anode may be stacked in this order. In addition, a passivation layer may be further included on the anode.

The passivation layer may be formed on the exposed surface of the organic photodiode and may absorb not only the protection of the organic photodiode but also the impact and stress generated when the substrate is removed.

1 illustrates an organic photodiode 100 according to an embodiment of the present invention. Referring to FIG. 1, an organic photodiode 100 includes a first electrode 10 and / or a second electrode 20 The excitons can be generated inside the active layer 30 when the active layer 30 absorbs light in the entire wavelength range. The excitons are separated into holes and electrons in the active layer 30, and the separated holes move to the anode side, which is one of the first electrode 10 and the second electrode 20, The current flows to the cathode side which is the other one of the two electrodes 20, and current can flow through the organic photodiode.

According to one embodiment of the present disclosure, the organic photodiode is a tandem structure.

According to an embodiment of the present invention, the organic layer includes a photoactive layer, and the photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer, and the p-type organic layer includes the polymer .

According to one embodiment of the present disclosure, the organic layer includes a photoactive layer, and the photoactive layer includes an electron donor material and an electron donor material, and the electron donor material includes the polymer.

According to one embodiment of the present invention, the electron-accepting material and the n-type organic compound layer may be selected from the group consisting of fullerene, fullerene derivative, vicoproin, semiconducting element, semiconducting compound, and combinations thereof. (6,6) -phenyl-C61-butyric acid-methylester) or PCBCR ((6,6) -phenyl-C61-butyric acid-cholesteryl ester), perylene perylene, polybenzimidazole (PBI), and 3,4,9,10-perylene-tetracarboxylic bis-benzimidazole (PTCBI).

According to one embodiment of the present disclosure, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ).

Bulk heterojunction means that the electron donor material and the electron acceptor material are mixed in the photoactive layer.

The organic photodiode according to one embodiment of the present invention is not limited to materials and / or methods in the art, except that a polymer containing the unit represented by the formula (1) is used as the photoactive layer of the organic photodiode Can be used.

In this specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in an organic electronic device. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; And conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, but are not limited thereto .

The method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . ≪ / RTI >

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming processes.

For example, the patterned ITO substrate is sequentially washed with a cleaning agent, acetone, and isopropyl alcohol (IPA), and then dried on a heating plate at 100 ° C to 150 ° C for 1 to 30 minutes, preferably 120 ° C for 10 minutes And when the substrate is completely cleaned, the surface of the substrate is hydrophilically modified.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

Pretreatment techniques for the anode electrode include a) surface oxidation using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet radiation in vacuum, and c) oxygen radicals generated by the plasma And the like.

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from the surface of the anode electrode or the substrate and to suppress the residual of moisture and organic matter as much as possible. At this time, the substantial effect of the pretreatment can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, the ITO substrate patterned after the ultrasonic cleaning is baked on a hot plate, dried well, then put into a chamber, and is irradiated with ozone generated by reaction of oxygen gas with UV light by operating a UV lamp The patterned ITO substrate can be cleaned.

However, the method of modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

The cathode electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Or a multilayer structure material such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The cathode may be deposited in a thermal evaporator having a degree of vacuum of 5 x 10 ^{< -7} > torr or less, but the method is not limited thereto.

The passivation layer may be formed of an inorganic material such as a silicon oxide film (SiOx) and a silicon nitride film (SiNx), or an organic material such as benzocyclobutene (BCB) and photo acryl, but is not limited thereto.

The passivation layer may be formed on the exposed surface of the organic photodiode using Plasma Enhanced Chemical Vapor Deposition (PECVD).

The hole transporting layer and / or the electron transporting layer material efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material may include poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid) (PEDOT: PSS), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but the present invention is not limited thereto.

The electron transport layer material may be electron-extracting metal oxides, specifically a metal complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but the present invention is not limited thereto.

The photoactive layer may be formed by dissolving a photoactive material such as an electron donor and / or an electron donor material in an organic solvent and then spin-coating, dip coating, screen printing, spray coating, doctor blade, brush painting or the like , But the present invention is not limited to these methods.

According to one embodiment of the present disclosure, there is provided a photoelectric pulse wave (PPG) sensor including the organic photodiode.

The polymer having the unit represented by the formula (1) according to one embodiment of the present invention has the maximum absorption wavelength in the absorption wavelength region of hemoglobin of 600 to 750 nm. Therefore, the organic photodiode including the polymer can be used as a photoelectric It can be applied to the volumetric pulse wave sensor.

The opto-electronic pulse-wave sensor includes a light source, and the light source may be any of those known in the art, and preferably, an LED, an OLED, or the like may be used.

The method for producing the polymer, the method for producing an organic photodiode including the same, and the production of a photoelectric pulse wave sensor including the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Production Example 1. Preparation of Polymer 1

               [Compound A] [Compound B]

                              [Polymer 1]

Compound A, compound B, toluene (5 mL) and dimethylformamide (3 mL) were added to a 100 mL flask under nitrogen to prepare a homogeneous solution. Nitrogen gas was added to the solution for 30 minutes, and then tetrakis (triphenylphosphine) palladium (0) (Pd (pph ₃ ) ₄ ) was added thereto. The mixture was stirred at 100 占 폚 for 72 hours. Then, 4-bromobenzotrifluoride (0.5 mL) was added to the solution, and the resulting solution was further stirred for 48 hours and then cooled to room temperature. The mixture was then poured into 100 mL of methanol. The precipitated polymer was obtained by filtration. The obtained polymer was subjected to Soxhlet extraction in the order of methanol, acetone, hexane and chloroform and chlorobenzene. The extract was concentrated in chloroform and chlorobenzene and then poured into methanol to precipitate the polymer. The precipitated polymer was again taken by filtration and dried under vacuum overnight. Purified Polymer 1 (368 mg, 93.8%) having a purple-black luster was obtained.

In chlorobenzene: 368 mg

GPC for the chlorobenzene fraction: Mn = 39300, PDI: 1.56

Figures 2 and 3 show the UV-vis absorption spectrum of the polymer 1. Specifically, the UV-vis absorption spectrum of FIG. 2 was measured by 1) UV-vis absorption spectrum of a sample (room temperature) in which the polymer 1 was dissolved in chlorobenzene, 2) the polymer 1 was dissolved in chlorobenzene, -vis absorption spectrum, and 3) UV-vis absorption spectrum of the sample obtained by dissolving Polymer 1 in chlorobenzene and heat-treated at 100 캜 was analyzed using a UV-Vis absorption spectrometer.

Specifically, the UV-vis absorption spectrum of FIG. 3 shows 1) a UV-vis absorption spectrum of a sample (room temperature) obtained by dissolving polymer 1 in chlorobenzene, 2) a UV-vis absorption spectrum of a film sample obtained by dissolving polymer 1 in chlorobenzene, -vis absorption spectrum, 3) The UV-vis absorption spectrum of the sample measured after heat treatment at 110 ° C was analyzed using a UV-Vis absorption spectrometer.

4 is a cyclic voltammetry graph of Polymer 1. Fig.

The results of the analysis of Polymer 1 according to FIGS. 2 to 4 are shown in Table 1 below.

λ _max (chlorobenzene)
(nm) ? _max (film)
(nm) λ _Op.BG
(eV) λ _Ec.BG
(eV) HOMO
(eV) Polymer 1 695 695 1.61 1.52 5.20

Production Example 2. Preparation of Polymer 2

            [Compound C] [Compound D]

                                      [Polymer 2]

Compound C, compound D, toluene (5 mL) and dimethylformamide (3 mL) were added to a 100 mL flask under nitrogen to prepare a homogeneous solution. Nitrogen gas was added to the solution for 30 minutes, and then tetrakis (triphenylphosphine) palladium (0) (Pd (pph ₃ ) ₄ ) was added thereto. The mixture was stirred at 100 占 폚 for 72 hours. Then, 4-bromobenzotrifluoride (0.5 mL) was added to the solution, and the resulting solution was further stirred for 48 hours and then cooled to room temperature. The mixture was then poured into 100 mL of methanol. The precipitated polymer was obtained by filtration. The obtained polymer was subjected to Soxhlet extraction in the order of methanol, acetone, hexane and chloroform and chlorobenzene. The extract was concentrated in chloroform and chlorobenzene and then poured into methanol to precipitate the polymer. The precipitated polymer was again taken by filtration and dried under vacuum overnight. Purified Polymer 2 (408 mg, 94%) having a purple-black luster was obtained.

In chlorobenzene: 408 mg

GPC for the chlorobenzene fraction: Mn = 31300, PDI: 1.71

Figures 5 and 6 show the UV-vis absorption spectrum of the polymer 2. Specifically, the UV-vis absorption spectrum of FIG. 5 is 1) the UV-vis absorption spectrum of a sample (room temperature) in which the polymer 2 is dissolved in chlorobenzene, 2) the polymer 2 is dissolved in chlorobenzene, -vis absorption spectrum, 3) Polymer 2 was dissolved in chlorobenzene, and the UV-vis absorption spectrum of the sample heat-treated at 100 캜 was analyzed using a UV-Vis absorption spectrometer.

Specifically, the UV-vis absorption spectrum of FIG. 6 is as follows: 1) the UV-vis absorption spectrum of a sample (room temperature) obtained by dissolving polymer 2 in chlorobenzene; 2) a UV-vis absorption spectrum of a film sample prepared by dissolving polymer 2 in chlorobenzene -vis absorption spectrum, 3) The UV-vis absorption spectrum of the sample after 2) was heat-treated at 110 ℃ and analyzed by UV-Vis absorption spectrometer.

7 is a cyclic voltammetry graph of Polymer 2. Fig.

The analytical results of Polymer 2 according to Figs. 5 to 7 are shown in Table 2 below.

λ _max (chlorobenzene)
(nm) ? _max (film)
(nm) λ _Op.BG
(eV) λ _Ec.BG
(eV) HOMO
(eV) Polymer 2 705 710 1.58 1.38 5.22

Example 1. Fabrication of organic photodiode

30 mg of each of Polymer 2 and PCBM was dissolved in 1 mL of dichlorobenzene (CB) to prepare a composite solution at 1: 1 (v / v). At this time, the concentration was adjusted to 3 wt%, and the organic photodiode had the structure of ITO / PEDOT: PSS / photoactive layer / LiF / Al. The glass substrate coated with 1.5 × 1.5 cm ² of ITO in a bar type was ultrasonically cleaned using distilled water, acetone, and 2-propanol. The ITO surface was ozone-treated for 10 minutes, and then PEDOT: PSS (AI4083) was spin coated at 5000 rpm for 60 seconds and heat treated at 150 占 폚 for 15 minutes. For the photoactive layer coating, Polymer 2 and PCBM composite solution were spin-coated at 500 rpm for 60 seconds and heat-treated at 180 ° C for 15 minutes. LiF was deposited to a thickness of 1 nm and Al was deposited at a rate of 1 Å / s with a thickness of 100 nm using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr to fabricate an organic photodiode.

Example 2. Fabrication of an organic photodiode

An organic photodiode was prepared in the same manner as in Example 1, except that the complex solution of polymer 2 and PCBM was spin-coated at 1000 rpm instead of 500 pm for coating the photoactive layer in Example 1.

Example 3 Fabrication of Organic Photodiode

An organic photodiode was prepared in the same manner as in Example 1, except that the complex solution of polymer 2 and PCBM was spin-coated at 2000 rpm instead of 500 pm for coating the photoactive layer in Example 1.

Example 4. Fabrication of an organic photodiode

An organic photodiode was prepared in the same manner as in Example 1, except that the complex solution of polymer 2 and PCBM was spin-coated at 3000 rpm instead of 500 pm for coating the photoactive layer in Example 1.

8 to 11 are graphs showing changes in voltage-current density according to the photoactive layer coating rmp of the organic photodiode according to Examples 1 to 4.

Measure response

The organic photodiodes of Examples 1 to 4 were irradiated with a light source (600 nm, 12 mW / cm ² ) to measure the response. 12 to 15, and the organic photodiode according to an embodiment of the present invention has excellent response in a wavelength region of 600 nm which is the absorption wavelength of hemoglobin, It can be seen that the organic photodiode can be applied to a photoelectric pulse wave sensor.

Measurement of transmittance by voltage

The light sources (600 nm, 12 mW / cm ² ) of the organic photodiodes of Examples 1 to 4 were irradiated and the dark current was measured according to the voltage applied to the photocurrent (I _light / I _dark ) . 16 to 19, I _light / I _dark was observed at a minus voltage in the organic photodiode according to an embodiment of the present invention, and it was confirmed that the organic light-emitting diode had excellent photodiode characteristics in a wavelength region of 600 nm which is an absorption wavelength of hemoglobin And the organic photodiode can be applied to a photoelectric pulse wave sensor.

10: first electrode
20: Second electrode
30: photoactive layer
100: Organic photodiode

Claims (10)

A polymer comprising a unit represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
n is an integer from 1 to 10,000,
R 1 to R 6 are the same or different from each other and each independently represents a linear or branched alkyl ester group; A substituted or unsubstituted straight or branched alkyl group; A substituted or unsubstituted straight or branched alkoxy group; A substituted or unsubstituted straight or branched alkylthio group; Or a substituted or unsubstituted straight or branched thioalkoxy group. [4] The compound according to claim 1, wherein R1 to R6 are the same or different and each independently represents a branched chain alkyl ester group; A branched alkyl group; Or a branched alkylthio group. The polymer of claim 1, wherein the terminal group of the polymer is an aryl group substituted with a haloalkyl group. The polymer of claim 1, wherein the polymer is selected from the following structures:

and n is an integer of 1 to 10,000. The polymer of claim 1, wherein the polymer has a maximum absorption wavelength at 500 nm to 800 nm. A first electrode;
A second electrode facing the first electrode; And
An organic photodiode including at least one organic layer provided between the first electrode and the second electrode,
Wherein at least one of said organic layers comprises a polymer according to any one of claims 1 to 5. < Desc / Clms Page number 13 > 7. The method of claim 6, wherein the organic layer comprises a photoactive layer,
The photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer,
Wherein the p-type organic layer comprises the polymer. 7. The method of claim 6, wherein the organic layer comprises a photoactive layer,
Wherein the photoactive layer comprises an electron donor material and an electron acceptor material,
Wherein the electron donor material comprises the polymer. The organic photodiode according to claim 8, wherein the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ). A photodiode-pulse-wave (PPG) sensor comprising an organic photodiode according to claim 6.

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