阅读说明：本技术 一种有机半导体激光产生方法及装置 (A kind of organic semiconductor laser generation method and device ) 是由 陶国华 谭云舒 于 2019-07-08 设计创作，主要内容包括：本发明公开了一种有机半导体激光产生方法及装置,所述方法包括：当有机半导体基态电子接收到电信号后,所述有机半导体基态电子激发到激发态；调控声子,通过电子与声子的直接耦合达到电荷传输态；通过电子与声子直接耦合发生单线态裂分,达到亚稳定的多激子中间态,产生粒子数反转；所述有机半导体基态电子不断从多激子中间态跃迁回基态,控制有机半导体层产生激光。本发明将单线态的多激子中间态最终转化为单线态基态,不需要系间窜越,转化效率高,通过对电声子耦合的调节,使激光的性能更加优异,可广泛应用于有机半导体激光器件领域。(The invention discloses a kind of organic semiconductor laser generation method and devices, which comprises after organic semiconductor ground state electron receives electric signal, the organic semiconductor ground state electron is energized into excitation state；Regulate and control phonon, charge transmitting state is reached by the direct-coupling of electronics and phonon；Singlet occurs by electronics and phonon direct-coupling to split point, reaches more exciton intermediate states of meta-stable, generation population inversion；The organic semiconductor ground state electron constantly returns ground state from more exciton intermediate state transition, and control organic semiconductor layer generates laser.More exciton intermediate states of singlet are eventually converted into singlet ground state by the present invention, do not need intersystem crossing, and high conversion efficiency keeps the performance of laser more excellent by the adjusting to electric phonon coupling, can be widely applied to organic semiconductor laser part field.)

1. a kind of organic semiconductor laser generation method, which is characterized in that the organic semiconductor laser generation method includes:

After organic semiconductor ground state electron receives electric signal, the organic semiconductor ground state electron is energized into excitation state；

Regulate and control phonon, charge transmitting state is reached by the direct-coupling of electronics and phonon；

Singlet occurs by electronics and phonon direct-coupling to split point, reaches more exciton intermediate states of meta-stable, generation population Reversion；

The organic semiconductor ground state electron constantly returns ground state from more exciton intermediate state transition, and control organic semiconductor layer, which generates, to swash Light.

2. organic semiconductor laser generation method according to claim 1, which is characterized in that described to pass through electronics and phonon Direct-coupling occurs singlet and splits point, reaches more exciton intermediate states of meta-stable, and generation population inversion specifically includes:

The Hamiltonian of system are as follows:

H=H_el+H_ph+H_el-ph；

Electron Hamiltonian amount are as follows: H_el=∑_k|k>E_k<k|+∑_l≠k|k>E_kl<l|；

Phonon Hamiltonian are as follows:

The sub- coupling terms of electroacoustic are as follows: H_el-ph=∑_k|k><k|∑_j(-c_kjQ_kj)；

Wherein, E_kFor the energy of k-th of electronic state, E_klFor the energy of k-th of electronic state coupling, l indicates first of electronic state, (Q_kj, P_kj) it is the point of j-th of phonon heating bath mould being coupled with k-th of electronic state in phase space, ω_kj, c_kjIts is corresponding respectively Frequency and coupling constant, N_bIt is the number of the heating bath mould coupled with each electronic state.

3. organic semiconductor laser generation method according to claim 2, which is characterized in that using classical mapping theory Activated state path method describes the sub- coupling of electroacoustic and dynamics, wherein the Hamiltonian of classical mapping theory is writeable are as follows:

Wherein,For the cloth inning of k-th of state, H_kkFor the Hamiltonian matrix element of k-th of state, (x_kx_l+ p_kp_l) Coherent coupling item between k-th of state and first of state cloth inning, H_klRelevant coupling between k-th of state and first of state Item is closed, (x, p), (Q, P) is the coordinate and momentum of classical electron and core freedom degree respectively, and γ is the ginseng for describing effective zero point energy Number, γ=1/2, or

4. organic semiconductor laser generation method according to claim 3, which is characterized in that the activated state path method The equation of motion are as follows:

Wherein,

B_mk, B_ml, B_lkFor its corresponding electron coefficient matrix, wherein H_mkThe Hami being coupled for m-th of state and k-th of state Pause and measures, H_act, P_act, Q_actThe respectively Hamiltonian of activated state, core momentum and coordinate.

5. organic semiconductor laser generation method according to claim 4, which is characterized in that the activated state is by following window Mouth function determines:

Wherein,

Wherein, An=2 γ is window width, and η (x) is step function, For electronic layout Variable, N_kFor quantum state number, k is state index.

6. organic semiconductor laser generation method according to claim 5, which is characterized in that choose phonon spectral density function For debye form:

Wherein, λ is Reorganization Energy, and ω is frequency, ω_cIt is characterized frequency.

7. organic semiconductor laser generation method according to claim 6, which is characterized in that the λ=100meV and ω_c =180meV.

8. organic semiconductor laser generation method according to claim 1, which is characterized in that more exciton intermediate states with Band gap between the excitation state is 1.5eV-2.5eV.

9. a kind of organic semiconductor laser generator, which is characterized in that the organic semiconductor laser generator includes:

Cathode, electron transfer layer, organic semiconductor thin-film layer, hole transmission layer, anode and the substrate set gradually from top to bottom；

The substrate is used to support film；The hole transmission layer and the electron transfer layer are respectively used to control hole and electronics It is transmitted in the organic semiconductor thin-film layer；The organic semiconductor thin-film layer is for generating laser after stimulated radiation occurs；

The HOMO highest occupied molecular orbital energy level of the hole transmission layer is injected in hole by the anode and the cathode, and the cathode will be electric Son injects the lowest unoccupied molecular orbital energy level of the electron transfer layer, the electronics of the electron transfer layer and the hole transmission layer Hole is migrated to the organic semiconductor thin-film layer, is excited spoke after the organic semiconductor thin-film layer receives electric signal It penetrates, stable exciton intermediate state is formed by electric phonon coupling and realizes population inversion, exciton is constantly from more exciton intermediate states Returning to ground state makes the organic semiconductor thin-film layer generate laser.

10. organic semiconductor laser generation method according to claim 9, which is characterized in that the organic semiconductor is thin Film layer is condensed-nuclei aromatics class compound.

Technical field

It is split point the present invention relates to organic semiconductor laser technology field more particularly to a kind of regulation organic semiconductor singlet The laser generation method and device of intermediate state.

Background technique

The light of atom-exciting radiation is known as laser, transits to high level from low-lying level after the Electron absorption energy in atom, When falling back to low-lying level from high level again, the energy discharged is released in the form of photon；From nineteen sixty American scientist Since the first ruby laser of Mei Man manufacture comes out, laser has been applied to electronics, ceramics, machine-building, aviation boat Numerous science and technology field such as it.

Organic semiconducting materials (conductive capability is between metal and insulator) Yin Qiyi forms a film, flexible area is big, light The various features such as excellent electrical property, energy solution processing, are widely used in laser material field at present.But organic semiconductor laser The usual pulsewidth of device is wider, and space quality is poor, and lacks good control measures.And general organic semiconductor laser is to pass through Singlet excited state transition returns ground state and generates laser, this kind of method is possible to generate the first triplet, and triplet absorbs meeting shadow Ring the intensity of laser.

The principle of machine semiconductor laser be common are as shown in Figure 1, being excited when excitation state electronics returns to ground state Radiation, thus generates laser.And the triplet excited state of energy production more high level can be absorbed by the T1 state that intersystem crossing obtains, Thus inhibit laser.

Summary of the invention

The technical problem to be solved in the present invention is that: laser pulsewidth is wider in the prior art, space quality is poor asks Topic.The present invention provides a kind of organic semiconductor laser generation method and device, so that particle occurs for organic semi-conductor intermediate state Number reversion, to generate laser.

The technical proposal for solving the technical problem of the invention is as follows:

A kind of organic semiconductor laser generation method, wherein the organic semiconductor laser generation method includes:

After organic semiconductor ground state electron receives electric signal, the organic semiconductor ground state electron is energized into excitation State；

Regulate and control phonon, charge transmitting state is reached by the direct-coupling of electronics and phonon；

Singlet occurs by electronics and phonon direct-coupling to split point, reaches more exciton intermediate states of meta-stable, generation grain Subnumber reversion；

The organic semiconductor ground state electron constantly returns ground state from more exciton intermediate state transition, and control organic semiconductor layer produces Raw laser.

The organic semiconductor laser generation method, wherein described that single line is occurred by electronics and phonon direct-coupling State is split point, and more exciton intermediate states of meta-stable are reached, and is generated population inversion and is specifically included:

The Hamiltonian of system are as follows:

H=H_el+H_ph+H_el-ph；

Electron Hamiltonian amount are as follows: H_el=∑_k| k > E_k< k |+∑_l≠k| k > E_kl< l |；

Phonon Hamiltonian are as follows:

The sub- coupling terms of electroacoustic are as follows: H_el-ph=∑_k| k > < k | ∑_j(-c_kjQ_kj)；

Wherein, E_kFor the energy of k-th of electronic state, E_klFor the energy of k-th of electronic state coupling, l indicates first of electronics State, (Q_kj, P_kj) it is the point of j-th of phonon heating bath mould being coupled with k-th of electronic state in phase space, ω_kj, c_kjIts is right respectively The frequency and coupling constant answered, N_bIt is the number of the heating bath mould coupled with each electronic state.

The organic semiconductor laser generation method, wherein retouched using the activated state path method of classical mapping theory State the sub- coupling of electroacoustic and dynamics, wherein the Hamiltonian of classical mapping theory is writeable are as follows:

Wherein,For the cloth inning of k-th of state, H_kkFor the Hamiltonian matrix element of k-th of state, (x_kx_l +p_kp_l) Coherent coupling item between k-th of state and first of state cloth inning, H_klRelevant coupling between k-th of state and first of state Item is closed, (x, p), (Q, P) is the coordinate and momentum of classical electron and core freedom degree respectively, and γ is the ginseng for describing effective zero point energy Number, γ=1/2, or

The organic semiconductor laser generation method, wherein the equation of motion of the activated state path method are as follows:

Wherein,

B_mk, B_ml, B_lkFor its corresponding electron coefficient matrix, wherein H_mkThe Hami being coupled for m-th of state and k-th of state Pause and measures, H_act, P_act, Q_actThe respectively Hamiltonian of activated state, core momentum and coordinate.

The organic semiconductor laser generation method, wherein the activated state is determined by following window function:

Wherein,

Wherein, Δ n=2 γ is window width, and η (x) is step function, For electricity Son layout variable, N_kFor quantum state number, k is state index.

The organic semiconductor laser generation method, wherein selection phonon spectral density function is debye form:

Wherein, λ is Reorganization Energy, and ω is frequency, ω_cIt is characterized frequency.

The organic semiconductor laser generation method, wherein the λ=100meV and ω_c=180meV.

The organic semiconductor laser generation method, wherein between more exciton intermediate states and the excitation state Band gap is 1.5eV-2.5eV.

To achieve the above object, the present invention also provides a kind of organic semiconductor laser generators, wherein described organic half Conductor Laser generation device includes:

The cathode that sets gradually from top to bottom, electron transfer layer, organic semiconductor thin-film layer, hole transmission layer, anode and Substrate；

The substrate is used to support film；The hole transmission layer and the electron transfer layer be respectively used to control hole with Electronics transmits in the organic semiconductor thin-film layer；The organic semiconductor thin-film layer swashs for generation after stimulated radiation occurs Light；

By the HOMO highest occupied molecular orbital energy level of hole injection hole transmission layer, the cathode will be electric for the anode and the cathode The lowest unoccupied molecular orbital energy level of son injection electron transfer layer, the hole of the electronics of the electron transfer layer and the hole transmission layer It is migrated to the organic semiconductor thin-film layer, stimulated radiation occurs after the organic semiconductor thin-film layer receives electric signal, led to It crosses electric phonon coupling and forms stable exciton intermediate state realization population inversion, exciton constantly returns to base from more exciton intermediate states State makes the organic semiconductor thin-film layer generate laser.

The organic semiconductor laser generator, wherein the organic semiconductor thin-film layer is condensed-nuclei aromatics class Close object.

The present invention regulates and controls organic semiconductor singlet by electric phonon coupling and splits point (singlet a fission, abbreviation SF) Intermediate state so that population inversion occurs for organic semi-conductor intermediate state, to generate laser, it is desirable to provide a kind of new has Machine semiconductor laser regulates and controls method, has much room for improvement to solve the problems, such as that existing laser pulsewidth is wider etc..

Detailed description of the invention

Fig. 1 is the schematic illustration that stimulated radiation occurs when excitation state electronics returns to ground state in the prior art and generates laser；

Fig. 2 is to regulate and control triplet excitons by energy transfer in the prior art to enhance the principle of laser intensity and illustrate Figure；

Fig. 3 is the flow chart of the preferred embodiment of organic semiconductor laser generation method of the present invention；

Fig. 4 is the schematic illustration of population inversion when laser generates in organic semiconductor laser generation method of the present invention；

Fig. 5 is the schematic diagram for regulating and controlling more exciton intermediates in organic semiconductor laser generation method of the present invention；

Fig. 6 be in the preferred embodiment of organic semiconductor laser generation method of the present invention Reorganization Energy be 200meV, 300K When S1 state, TT state, CT state with phonon regulate and control time change schematic diagram；

Fig. 7 be in the preferred embodiment of organic semiconductor laser generation method of the present invention Reorganization Energy be 100meV, 300K When S1 state, TT state, CT state with phonon regulate and control time change schematic diagram；

Fig. 8 is the structure principle chart of the preferred embodiment of organic semiconductor laser generator of the present invention.

Specific embodiment

To make the objectives, technical solutions, and advantages of the present invention clearer and more explicit, right as follows in conjunction with drawings and embodiments The present invention is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to It is of the invention in limiting.

Organic semiconductor laser generation method described in present pre-ferred embodiments, as shown in figure 3, a kind of organic semiconductor Laser generation method, wherein the organic semiconductor laser generation method the following steps are included:

Step S10, after organic semiconductor ground state electron receives electric signal, the organic semiconductor ground state electron excitation To excitation state；

Step S20, regulate and control phonon, charge transmitting state is reached by the direct-coupling of electronics and phonon；

Step S30, singlet occurs by electronics and phonon direct-coupling to split point, reaches among more excitons of meta-stable State generates population inversion；

Step S40, the described organic semiconductor ground state electron constantly returns ground state from more exciton intermediate state transition, controls organic half Conductor layer generates laser.

As shown in Figure 4 and Figure 5, population inversion process when laser of the present invention generates are as follows: when organic semiconductor ground state electron After optical signal, the organic semiconductor ground state electron is energized into excitation state S1；Regulation phonon (regulation method is optional, such as Pass through temperature control or light excitation regulation.), charge transmitting state CT is reached by the direct-coupling of electronics and phonon, then by electronics with The direct-coupling of phonon occurs singlet and splits point, reaches more exciton intermediate states of the singlet of meta-stable, generation population inversion, Ground state is returned in electronics constantly transition at this time, to generate laser.

Wherein, singlet, which is split, point refers in singlet (S₁) exciton be in ground state (S in adjacent₀) exciton it is mutual Effect, passes through more exciton intermediate states¹(TT), two independent triplet excitons (T are generated₁) special process in conversion process, can It is expressed from the next:

Regulate and control organic semiconductor singlet by electric phonon coupling and splits point centre of (singlet fission, abbreviation SF) State, so that population inversion occurs for organic semi-conductor intermediate state, to generate laser.

To illustrate to regulate and control the basic principle that singlet state splits point intermediate state by Spin-orbit interaction, by the Hamiltonian H of system It is written as such as lower class spin-boson form:

H=H_el+H_ph+H_el-ph；

Electron Hamiltonian amount is H_el=∑_k| k > E_k< k |+∑_l≠k| k > E_kl< l |,

Phonon Hamiltonian is

The sub- coupling terms of electroacoustic are H_el-ph=∑_k| k > < k | ∑_j(-c_kjQ_kj)。

Wherein, E_kFor the energy of k-th of electronic state, E_klFor the energy of k-th of electronic state coupling, (Q_kj, P_kj) be and kth Point of the corresponding vibration mode of j-th of phonon of a electronic state coupling in phase space, ω_kj, c_kjRespectively its corresponding frequency and Coupling constant, N_bIt is the number of the heating bath mould coupled with each electronic state.

The sub- coupling of electroacoustic is described using the activated state path method based on Meyer-Miller classics mapping theory below and is moved Mechanics.The Hamiltonian of classical mapping theory is writeable are as follows:

Wherein,For the cloth inning of k-th of state, H_kkFor the Hamiltonian matrix element of k-th of state, (x_kx_l +p_kp_l) Coherent coupling item between k-th of state and first of state cloth inning, H_klRelevant coupling between k-th of state and first of state Item is closed, (x, p), (Q, P) is the coordinate and momentum of classical electron and core freedom degree respectively, and γ is the ginseng for describing effective zero point energy Number.Optionally, γ=1/2, or

Further, the equation of motion of the activated state path method are as follows:

Wherein,

B_mk, B_ml, B_lkFor its corresponding electron coefficient matrix, wherein x_mAnd x_kRespectively m-th of electronics, k-th electronics Coordinate, p_mAnd p_kThe momentum of respectively m-th of electronics, k-th electronics, δ_mkIt is a kind of operation function of mathematics；H_mkFor m-th of state The Hamiltonian being coupled with k-th of state, H_act, P_act, Q_actThe respectively Hamiltonian of activated state, core momentum and coordinate.

The activated state is determined by following window function:

Wherein,

Wherein, Δ n=2 γ is window width, and η (x) is step function, For electricity Son layout variable, N_kFor quantum state number, k is state index.

Choosing phonon spectral density function without loss of generality is debye form:

Wherein, λ is Reorganization Energy, and ω is frequency, ω_cIt is characterized frequency.

In the present embodiment, λ=100meV (meV expression million-electron-volt, energy unit) and ω is taken_c=180meV, the group It is 0.6 that conjunction, which provides the Huang-Rhys factor, is consistent in spectrum experiment.Compare for convenience, which is known as standard state.

Below using ten aggressiveness of pentacene as embodiment, illustrate Spin-orbit interaction regulatory mechanism.System includes 52 electronic states (10 singlets (S0S1/S1S0), 28 charge transmitting states (CT), exciton intermediate state (TT) more than 14).State energy level takes relatively Value is E (S1)=0.0eV, E (CT)=0.3eV, E (TT)=0.17eV.Each electronic state coupling phonon number can use 1-10000 It is a.

As shown in Figure 6, Figure 7, it by the above method, is derived according to calculating and analogue data, the present embodiment can be obtained as follows Data: by being combined regulation to phonon, change its characteristic frequency and Reorganization Energy, the TT state cloth inning relative to standard state 54% is increased to by 34% in 500fs.It should be noted that this example is only to show to obtain by regulating and controlling Spin-orbit interaction Expected intermediate state cloth inning is obtained, used parameter is not indicated and intermediate state cloth inning is optimal.Under another group of Parameter Conditions, Equilibrium distribution can be rebuild, intermediate state is inhibited, S1 state is made to reach 60% in 500fs.

Further, as shown in figure 8, being based on above-mentioned organic semiconductor laser generation method, the present invention is further correspondingly provided A kind of organic semiconductor laser generator, the organic semiconductor laser generator include:

Cathode 1, electron transfer layer 2, organic semiconductor thin-film layer 3, hole transmission layer 4, the sun set gradually from top to bottom Pole 5 and substrate 6.

Wherein, the substrate 6 is used to support film；4 layers of the hole transport and the electron transfer layer 2 are respectively used to control Hole processed and electronics transmit in the organic semiconductor thin-film layer 3；The organic semiconductor thin-film layer 3 is for being excited spoke Laser is generated after penetrating.

Specifically, the HOMO highest occupied molecular orbital energy of the hole transmission layer 4 is injected in hole by the anode 5 and the cathode 1 Grade (HOMO energy level), the cathode 1 by the lowest unoccupied molecular orbital energy level (lumo energy) of electron transfer layer 2 described in electron injection, The hole of the electronics of the electron transfer layer 2 and the hole transmission layer 4 is migrated to the organic semiconductor thin-film layer 3, works as institute It states after organic semiconductor thin-film layer 3 receives electric signal and stimulated radiation occurs, formed by electric phonon coupling among stable exciton State realizes population inversion, and exciton constantly returns to ground state from more exciton intermediate states and the organic semiconductor thin-film layer 3 is produced Raw laser.

Further, when needing to close laser, by regulating and controlling electric phonon coupling exciton intermediate state is reduced, ground state electricity Sub- content increases, to close laser.The advantage of the process is, generation¹(TT) state is singlet, is easier to be converted into low energy The singlet of grade, to generate laser.

The organic semiconductor thin-film layer 3 can be condensed-nuclei aromatics class compound, such as pentacene analog,¹(TT) state Band gap between S1 state can be 1.5eV-2.5eV (wherein, eV indicates electron-volt, is energy unit).

The electron transfer layer 2 can split that point quantum yield is high and benzene derivative for the singlets such as pentacene.

The HOMO energy level of the hole transmission layer 4, the lumo energy of electron transfer layer 2 should select the energy of organic semiconductor layer The grade preferable material of matching degree.

6 material of substrate is the compound of organic material, inorganic material or organic material and inorganic material.

In conclusion the present invention provides organic semiconductor laser production method and device, which comprises when organic half After conductor ground state electron receives electric signal, the organic semiconductor ground state electron is energized into excitation state；Regulate and control phonon, passes through electricity The direct-coupling of son and phonon reaches charge transmitting state；Singlet occurs by electronics and phonon direct-coupling to split point, reaches Asia Stable more exciton intermediate states generate population inversion；The organic semiconductor ground state electron constantly jumps from more exciton intermediate states Ground state is moved back to, control organic semiconductor layer generates laser.The present invention passes through electric phonon coupling, so that more swashing in organic semiconductor Sub- intermediate ratio increases.By the adjusting to electric phonon coupling, keeps the performance of laser more excellent, can be widely applied to Machine semiconductor laser field.

It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.