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Fabrication and Application of Photonic Crystal Biochemical Sensor

Huipeng Hou , Axin Liang , Bo Tang , Zongkun Liu , Aiqin Luo

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (7) : 1126 -1137.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (7) : 1126-1137 DOI: 10.7536/PC200711
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Fabrication and Application of Photonic Crystal Biochemical Sensor
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Abstract

Photonic crystal biochemical sensing is a promising analytical method which amplifies or converts biochemical signals into photoelectrically readable signals and performs quantitative or semi-quantitative analysis by instruments or naked eyes, based on the structural characteristics of photonic crystals. This review mainly focuses on the three aspects of the photonic crystal biochemical sensor: material selection and fabrication, sensing mechanism, design and application. Firstly, in terms of material selection and fabrication, this article reviews the monodisperse colloidal nanoparticles, electromagnetic composite colloidal nanoparticles, nanowires, metal organic frameworks and so on. Secondly, the sensing mechanism is briefly introduced from three aspects: structure color, slow light effect and photoelectric conversion mechanism. Further, the design and application of visible photonic crystal biochemical sensor, fluorescence enhanced photonic crystal biochemical sensor, Raman enhanced photonic crystal biochemical sensor, evanescent wave enhanced photonic crystal biochemical sensor, surface infrared absorption enhanced photonic crystal biochemical sensor and photoelectric signal enhanced photonic crystal biochemical sensor are reviewed, based on the perspective of interaction effect of photonic crystal and light. Finally, the future of photonic crystal biochemical sensor is prospected.

Contents

1 Introduction

2 Material selection and fabrication of photonic crystal biochemical sensor

2.1 Monodisperse colloidal nanoparticles

2.2 Electromagnetic composite colloidal nanoparticles

2.3 Nanowires

2.4 Metal organic frameworks

2.5 Other materials

3 Sensing mechanism of photonic crystal biochemical sensor

3.1 Structure color

3.2 Slow light effect

3.3 Photoelectric conversion mechanism

4 Design and application of photonic crystal biochemical sensor

4.1 Visible photonic crystal biochemical sensor

4.2 Fluorescence enhanced photonic crystal biochemical sensor

4.3 Raman enhanced photonic crystal biochemical sensor

4.4 Evanescent wave enhanced photonic crystal biochemical sensor

4.5 Surface infrared absorption enhanced photonic crystal biochemical sensor

4.6 Photoelectric signal enhanced photonic crystal biochemical sensor

4.7 Other photonic crystal biochemical sensors

5 Conclusion and outlook

Graphical abstract

Keywords

photonic crystal biochemical sensor / visible assay / fluorescence enhancement / molecular imprinting / metal organic frameworks

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Huipeng Hou, Axin Liang, Bo Tang, Zongkun Liu, Aiqin Luo. Fabrication and Application of Photonic Crystal Biochemical Sensor. Progress in Chemistry, 2021, 33(7): 1126-1137 DOI:10.7536/PC200711

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1 Introduction

In the process of species evolution, organisms have gradually formed natural Photonic crystals (PCs) physiological structures to reproduce and avoid danger, such as the reversible body color of Pentapodus paradiseus, the bright wings of Chalcopterix rutilans, and the vivid structural color of Cystoseira tamariscifolia[1⇓⇓⇓~5]. Inspired by the structure of natural photonic crystals, synthetic photonic crystals have attracted the attention of researchers.
Photonic crystals are materials composed of two or more media with different refractive indices (n) arranged periodically in space. Photons in the Photonic Band-Gap (PBG) frequency range cannot propagate in any direction[5]. In addition, photonic crystals have proven to be a promising platform for biochemical sensing analysis, and when combined with other optical technologies can exhibit the ability to enhance local electromagnetic fields[6]. At present, photonic crystals have been widely used in biochemical sensing, anti-counterfeiting encryption, optical fiber communication and optoelectronic devices[7⇓⇓~10][11,12][13,14][15⇓⇓⇓⇓~20].
The development of sensitive, efficient, intuitive, portable and multiplexed biochemical sensors has always been the goal of researchers. Due to the unique photonic bandgap structure, photonic crystals provide new possibilities for the development of biochemical sensor technology. Photonic crystal biochemical sensor is one of the common analytical methods in the fields of food safety, biomedicine, clinical diagnosis and environmental pollution[21][8][7,22,23][24,25][26]. In recent years, there have been a lot of reports on the self-assembly methods of photonic crystals and the types of stimulus response, but there are few reports on the research progress of photonic crystal biochemical sensors from the perspective of the interaction effect between photonic crystals and light[27][26,28⇓~30]. In this paper, the material selection, construction and sensing mechanism of photonic crystal biosensors are reviewed.A visible photonic crystal biochemical sensor, a fluorescence enhanced photonic crystal biochemical sensor, a Raman enhanced photonic crystal biological sensor, an evanescent wave enhanced photonic crystal biological sensor,The design and application status of surface infrared absorption enhanced photonic crystal biochemical sensors and photoelectric signal enhanced photonic crystal biochemical sensors are summarized and prospected.

2 Material Selection and Construction of Photonic Crystal Biochemical Sensor

The photonic crystal biochemical sensor is mainly composed of two parts: a stimulus response unit and a signal conversion unit. The stimulation response unit refers to a part which amplifies or responds to an external stimulation signal, namely a photonic crystal; The signal conversion unit is to convert the external stimulus into a photoelectric readable signal, mainly through the naked eye or instruments to achieve the detection of the target. Therefore, the key to the construction of photonic crystal biochemical sensors lies in the preparation of photonic crystals and the selection of detection methods.
So far, various efforts have been made to prepare photonic crystals. The materials commonly used in the preparation of photonic crystals include monodisperse colloidal particles, electromagnetic composite colloidal particles, nanowires and metal-organic frameworks.

2.1 Monodisperse colloidal particle

Colloidal particles, such as silica (SiO2), polystyrene (PS) and polymethyl methacrylate (PMMA), which are easy to synthesize, controllable in particle size and good in monodispersity, are the most widely studied and applied materials for the preparation of photonic crystals.
Vertical deposition self-assembly of monodisperse colloidal particles (fig. 1A) using capillary forces in conjunction with surface tension has proven to be the most versatile laboratory method for the fabrication of three-dimensional (3D) photonic crystals[31]. In our research group, the glass slides treated with piranha solution were vertically immersed in 2 wt% SiO2 ethanol solution, and placed at 30 ℃ for several days. After the ethanol was evaporated, photonic crystals were obtained on both sides of each glass slide[32]. Similarly, Yan et al. Prepared polymethyl methacrylate (PMMA) photonic crystals by vertical deposition self-assembly, and removed PMMA colloidal particles by toluene etching to obtain PMMA photonic crystals with inverse opal structure[33]. However, the uncontrollable evaporation rate of the solvent and the gravity of the colloidal particles themselves may lead to the failure of self-assembly of colloidal particles[34]. In addition, the concentration of colloidal particles changes significantly during the evaporation of the solvent, which may have an impact on the number of self-assembled layers of photonic crystals[35].
Ozin et al. Proposed stirring to assist solvent (ethanol) evaporation to overcome the disadvantage of colloidal particles (SiO2) sedimentation, but magnetic stirring may lead to air-solution-colloidal particles interface vibration, affecting the effect of self-assembly of colloidal particles[34].
In order to overcome the above problems, Gu et al. Constructed photonic crystals in a short time by using the slow vertical pulling substrate method (Fig. 1b)[35]. Because the speed of substrate lifting is obviously higher than the speed of solvent (water) volatilization and the speed of polystyrene (PS) colloid particle natural sedimentation,The method not only can overcome the problem of non-uniform thickness of the photonic crystal growth caused by solvent volatilization and colloid particle sedimentation, but also can accurately control the thickness of the photonic crystal by controlling the concentration of the colloid particles and the pulling speed. However, this method requires a high concentration of colloidal particles to ensure the smooth progress of self-assembly.
Zhou et al. Improved the above method and proposed a method of using a micro peristaltic pump to slowly pump the solution from the bottom to achieve stable self-assembly of polystyrene colloidal particles (PS)[36]. On the one hand, the fixed substrate can avoid the risk of shaking; On the other hand, a peristaltic pump can slowly pump the solution away at a constant flow rate to minimize the change in the concentration of colloidal particles due to sedimentation. In that method, the descend speed of the liquid level of the solution is adjusted by the pump speed of a peristaltic pump and the cross-sectional area of a container, so that the method is more precise and wider in application range than a slow vertical pulling method.
In recent years, two-dimensional (2D) photonic crystals, which are easier and faster to prepare, have come into the field of vision of researchers[37]. In the case of a 2D polystyrene photonic crystal, about 0.2 mL of a mixture of 20 wt% polystyrene solution and n-propanol (V/V: 3:1) is slowly injected into a glass dish filled with water. Due to the low surface tension of n-propanol, the polystyrene colloidal particles diffuse to the water surface until they cover the entire surface. 2D photonic crystals were then obtained by immersing the piranha solution treated slide in water and lifting it at an angle of 20 ° (Fig. 1 C)[38].
In addition, spin coating is also a fast and reliable method for the preparation of photonic crystals. In this method, the thickness of the photonic crystal is controlled by changing the concentration of the colloidal particle suspension or the rotation speed of the substrate. Colodrero et al. achieved periodic control of the refractive index of photonic crystals by alternately depositing different kinds of nanoparticles by spin coating[39].

2.2 Lectromagnetic composite colloid particle

It is desirable to construct composite colloidal particles with electromagnetic properties and to construct photonic crystals by controlling their motion direction according to needs through simple external stimuli. Of all external stimuli, magnetic fields with immediate action are commonly used. Ge et al. Dispersed superparamagnetic Fe3O4@SiO2 colloidal particles in resin droplets, and self-assembled them into periodically arranged one-dimensional photonic crystal chains under the balance of repulsion and attraction (Fig. 1D). Due to the repulsion between photonic crystal chains caused by external magnetic field, the interval between adjacent photonic crystal chains is usually several microns[40]. This is immediately followed by ultraviolet (UV) light curing to encapsulate the photonic crystal chains in the resin. Because the superparamagnetic one-dimensional photonic crystal chain is aligned along the direction of the magnetic field, the structural color of the superparamagnetic one-dimensional photonic crystal chain can be adjusted by changing the direction of the magnetic field and adjusting the incident angle of light.
Li et al. Coated a layer of silica (SiO2) with a thickness of about 25 nm on the outside of Prussian blue nanocubes (PB), and prepared Fe3O4@SiO2 nanocubes by polyol reduction[43]. Next, they sealed Fe3O4@SiO2 nanocubes in capillaries, allowing light to enter along the edges of the capillaries. Under the action of an external magnetic field, the one-dimensional photonic crystal chain will produce a diffraction pattern with continuous color bands. For example, when the direction of the photonic crystal chain is parallel to the direction of the incident light, blue light (120 °), green light (105 °), yellow light (90 °), orange light (75 °) and red light (60 °) can be observed in turn by changing the reflection angle.
Compared with the magnetic field, the electric field has the advantage of periodic regulation. Under the action of the electric field, the charged particles begin to move towards the oppositely charged electrode until the relaxation force is balanced with the electrophoretic force. Yang et al. prepared periodically arranged photonic crystals (Fig. 1e) by directional migration of polystyrene particles modified by phenolic groups with negative charges on the surface induced by electric field. The directional migration of charged particles led to the change of lattice spacing of photonic crystals, accompanied by visible structural color changes[41]. Lee et al. Successfully prepared charged poly (t-butyl methacrylate) microspheres and stabilized them by charged reverse micelles of sodium bis (2-ethylhexyl) sulfosuccinate (1 wt%) in a non-polar organic fluid. When the mass percentage of the microspheres reached about 30%, photonic crystals with electrically tunable structural colors were formed[44].

2.3 Nanowire

The design of chiral photonic crystals mainly originates from two different thinking orientations, namely, structural chirality and medium chirality[5]. Among them, structural chiral photonic crystals generally refer to a kind of photonic crystals whose optical activity comes from the microscopic helical skeleton of the object itself. Tang Zhiyong et al. produced large-area highly aligned nanowires, transferred them to quartz plates from bottom to top by Langmuir-Schaefer method, rotated them layer by layer, accurately regulated and controlled, and synthesized chiral photonic crystals with adjustable optical rotation and controllable optical rotation direction (Fig. 1 f)[42]. By the method, the nano material with excellent optical and electromagnetic properties is expected to be doped into the chiral photonic crystal, and a new material is provided for biochemical sensing analysis of the photonic crystal[42].

2.4 Metal-organic framework

High porosity, high stability, large specific surface area and highly tunable morphology and size make Metal Organic Frameworks (MOFs) an ideal support material in the field of biochemical sensing[45]. Li Guangtao et al. First soaked the polystyrene photonic crystal template with the precursor solution of copper pyromellitic acid (HKUST-1), then evaporated the solvent to crystallize HKUST-1, and finally used tetrahydrofuran (THF) to selectively dissolve the polystyrene template to construct Inverse opal photonic crystals (IOPCs) with 3D macroporous structure[46].
Although MOFs as the filling materials of photonic crystals have made satisfactory progress, there are few reports on the direct preparation of photonic crystals by using MOFs as photonic crystal colloidal particles. Avci et al. Dropped an aqueous solution of a zeolitic imidazolate framework (ZIF-8) capped with cetyltrimethylammonium bromide (CTAB) onto a clean glass slide and evaporated the water at 65 ℃ to successfully prepare the ZIF-8 photonic crystal[47]. Chen Su et al. Prepared hydrophilic PAMAM @ ZIF-8 monodisperse colloidal particles by using zeolite imidazole ester skeleton (ZIF-8) modified by polyamidoamine (PAMAM) dendrimers, and directly assembled photonic crystals with bright structural colors on the surface of reduced graphene oxide (rGO)[48].

2.5 Other

In addition to the materials discussed above, quantum dots (QDs), metals (alloys), and metal oxides (sulfides, halides) such as Au, Bi-Sb, TiO2, and ZnS are also used in the preparation of photonic crystals[49]. Shi et al. Prepared a low-angle-dependent photonic crystal film by vertical deposition of self-assembled CdS@SiO2 core-shell nanoparticles with high refractive index, and successfully used it for visual detection and removal of uranyl ions[50].
In addition, new nano-materials with regular morphology and size are expected to be used to prepare photonic crystals, which still needs to be further explored.

3 Sensing Mechanism of Photonic Crystal Biochemical Sensor

The main method for constructing the photonic crystal biochemical sensor is to prepare a photonic crystal with an adjustable photonic band gap from a stimulus-responsive material by direct construction or later filling, and realize different responses to biochemical signals by changing the type of the stimulus-responsive material or a detection method[51].

3.1 Structural color principle

The visible color change is the result of the interaction of light and mass, which can be divided into chemical color and structural color according to the difference of action mechanism. Chemical color is related to the absorption of light by pigments contained in organisms, while structural color is the color produced by refraction, reflection, diffraction or interference of light by the microstructure of the object itself[5].
The response of photonic crystal biochemical sensor to external stimulus signal is mainly based on the Bragg diffraction peak shift of photonic crystal. The Bragg diffraction wavelength of the photonic crystal conforms to the Bragg-Snell diffraction equation:
λ = 2 d / m (n 2 - n d 2 si n 2 θ ) 1 / 2
Where lambda is the Bragg diffraction wavelength; And d is a lattice constant; And m is the diffraction order; And n is that weight average refractive index; The $n_d$ is that refractive index of the lattice point; Theta is the angle of incidence of the light[52].
As shown in fig. 2, the Bragg diffraction peak of the photonic crystal can be displaced by changing the lattice constant (d) of the photonic crystal or the incident angle of light (θ) through an external stimulus signal. When the Bragg diffraction peak of the photon crystal is located in the visible light region and the displacement value is large, the macroscopic structural color change is visible to the naked eye.

3.2 Slow Light Effect

Photonic Band-Gap (PBG) is one of the most fundamental properties of Photonic crystals. The introduction of defects will destroy the periodic variation of the dielectric constant of the photonic crystal and produce the corresponding defect modes in the PBG[53,54]. Near the frequency of the defect mode, the group velocity of light is greatly reduced and slow light is formed[54].
There are three slow light mechanisms in the photonic crystal waveguide: (1) the resonance caused by the Fabry-Perot modes generated by the forward propagating light and the light specularly reflected by the waveguide boundary is transverse, as shown in fig. 3A; (2) As shown in fig. 3B, the Littrow mode is generated when the phases of the forward propagating guided mode and the backward propagating guided mode coincide at the boundary of the Brillouin zone; (3) As shown in Fig. 3C, the anti-crossing mode is generated in the Brillouin zone, which is caused by the interaction of the transmission guided modes of different orders, and is formed when the phase condition is satisfied at a certain position in k-space[53,54].
The slow light effect of photonic crystals leads to the longer interaction time between the light and the gain material, resulting in the optical gain phenomenon, which has broad application prospects in the field of optical detection[54].

3.3 Photoelectric conversion mechanism

The photoelectric signal enhanced photonic crystal biochemical sensor comprises a photoelectric conversion process and an electrochemical process. As shown in Figure 4, if the electrons get enough energy to break free of the nucleus, the valence band electrons jump to the conduction band, creating positively charged holes and electrons. The follow reactions may ensue: (1) as shown in fig. 4A, that photo-generated electron-hole migrate to the interface between the electrode and the electrolyte solution to undergo an oxidation-reduction reaction; (2) As shown in fig. 4B, the photogenerated electrons return to the valence band and recombine with the holes to be converted into energy and emitted; (3) As shown in Fig. 4C, the photogenerated electron-hole pairs form a photocurrent under the action of an external electric field[55,56].
The combination of photonic crystals and electrochemical sensors has several advantages: (1) the large specific surface area of photonic crystals provides multiple active sites for photoelectrochemically active substances; (2) the high porosity of the inverse opal photonic crystal is favorable for the movement of photoelectrochemically active species or charges[41]; (3) The slow light effect of photonic crystals can increase the interaction time of light and mass, resulting in optical gain phenomenon[54]. Photoelectric signal enhanced photonic crystal biochemical sensors have the advantages of electrochemical sensors and the characteristics of photonic crystal biochemical sensors, and have a wide range of applications in the field of biochemical sensing.

4 Design and Application of Photonic Crystal Biochemical Sensor

Photonic Crystal (PC) Biochemical sensor is a kind of sensor that can amplify or convert biochemical stimulation signal into photoelectric readable signal.Biochemical sensors can be classified into visual photonic crystal biochemical sensors, fluorescence enhanced photonic crystal biochemical sensors, Raman enhanced photonic crystal biochemical sensor, evanescent wave enhanced biochemical sensor, surface infrared absorption enhanced biochemical sensor and photoelectric signal enhancement biochemical sensor.

4.1 Visible photonic crystal biochemical sensor

The visible photonic crystal biochemical sensor can convert biochemical stimulation signals into visible light signals, and perform semi-quantitative analysis by establishing a standard colorimetric card, thereby avoiding the tedious data post-processing work of the traditional biochemical sensor. Visible light is an electromagnetic wave that can be perceived by human eyes, and its wavelength is generally between 400 and 760 nm. When the Bragg diffraction peak (λ) of the photonic crystal is located in the visible light region, its structural color can be perceived by the naked eye.
The alcohol sensor has important practical value in the aspects of monitoring the quality of alcoholic drinks, cracking down on underage drinking and real-time detection of drunk driving[57]. Meng Zihui et al. Used capillary action to infiltrate methyl cellulose solution into the gap of polymethyl methacrylate (PMMA) photonic crystal array, overcome the defect of short shelf life of traditional photonic crystal film, and constructed a visible photonic crystal film (CPCFS) with optical activity and physical toughness after six months of storage at room temperature[58]. The CPCFS initially appears blue and turns green after immersion in ethanol. In order to explore the response mechanism of CPCFS, they immersed it in n-propanol (n = 1.3856), ethanol (n = 1.3614), n-butanol (n = 1. 3993) and isopropanol (n = 1. 3775) respectively, and the red shifts were 76, 73, 63 and 56 nm respectively. The study found that PMMA colloidal particles swelled in alcohol solution, and the red shift of CPCFS was caused by the change of refractive index of solvent and the volume expansion of photonic crystal. The sensor extends the application of CPCFS in the field of visual detection of alcohol, but it can not avoid the interference of water.
Yu et al. Developed a visible photonic crystal biosensor that can clearly identify ethanol-water mixtures with ethanol content between 0% and 40% by changing the contact angle of ethanol-water solution by adjusting the ratio of hydrophobic silane coupling agent (ACE) and hydrophilic silane coupling agent (PEG) (1:0, 1:1, 5:1, 10:1, 25:1 and 0:1) in the silane mixture of SiO2 photonic crystal glass rod (IOF)[57].
As shown in Figure 5, they isolated seven different areas on the IOF sensor with six different ratios of silane mixtures and water, which became colorless when wetted by ethanol-water solution and returned to their structural color when the ethanol-water solution evaporated[57]. The sensor combines the color of the photonic crystal structure with the wettability, meets the requirements of intuitive and instant on-site detection of ethanol, and has broad application prospects in the detection of biochemical molecules in solution.
Specificity is the bottleneck of photonic crystal biochemical sensors in biochemical applications. Surface molecularly imprinted polymer (SMIP) has the advantages of high stability, good affinity, excellent specific recognition ability, low production and storage costs, high reuse rate and strong environmental tolerance[59]. In order to improve the specificity of photonic crystal biosensors, SMIP was introduced.
By immersing the molecularly imprinted pre-polymerization solution into the sandwich-structured photonic crystal template and using UV light to initiate polymerization, and then using HF and eluent to remove the SiO2 particles and template respectively (Fig. 6), the visual molecularly imprinted photonic crystal film with inverse opal structure was constructed[32]. After specific binding with melamine, the Bragg diffraction peak was red-shifted and the color changed from green to red.The limit of detection (LOD) was about 0. 01 μmol/L, which was much lower than the limit value of melamine in infant formula set by the Ministry of Health.
The demand for visual detection of biomacromolecules is increasing in clinical diagnosis and other fields. Meng Zihui et al. Achieved the purpose of visual detection of bovine hemoglobin (Hb) by constructing a molecularly imprinted photonic crystal biochemical sensor[61]. Hb was immobilized on the surface of SiO2 by metal coordination bonds to form a surface molecularly imprinted polymer (MIP), which was dispersed in deionized water and deposited vertically to form a photonic crystal sensor (MICA) with opal structure. When MICA specifically binds to Hb, its color changes from navy blue to pearl blue, which makes the visual detection of Hb in complex matrices possible.
Deng et al. Constructed a photonic crystal molecularly imprinted contact lens with inverse opal structure, which allows users to monitor the release and adsorption of eye drops in real time according to the color change of the contact lens visible to the naked eye, and has high practical value[62].
Enantiomers have great differences in biological metabolism, physiological toxicity and pharmacological activity, so chiral recognition plays an important role in the fields of biochemical analysis, clinical diagnosis and chemical pharmacy[63,64].
Meng Zihui et al. infiltrated L-uracil (L-KYN) molecularly imprinted prepolymer solution into 2D polystyrene colloidal array, and obtained visible photonic crystal biochemical sensor (PCCA) after UV photopolymerization and elution of template[65]. With the increase of L-KYN concentration from 50 nmol/L to 1 000 nmol/L, the distance between colloidal particles decreased by 85 nm, and the structural color of PCCA changed from red to green. The change of the distance between the colloidal particles of D-KYN is only 23 nm, which proves that PCCA has excellent chiral recognition ability.
The visual molecular imprinting photonic crystal biochemical sensor, which integrates the functions of molecular specific targeting recognition and signal transduction, has been proved to be an intuitive and visual method for biochemical molecular analysis and detection, as shown in Table 1.

4.2 Fluorescence-enhanced photonic crystal biochemical sensor

Weak fluorescence signal is still a challenge for trace detection of biochemical molecules and fluorescence imaging technology[6]. The slow light effect of photonic crystals can significantly increase the effective path length of light, which is conducive to the interaction of light and mass. When the diffraction peak of photonic crystals is close to or consistent with the excitation or emission wavelength of fluorescent substances, the fluorescence signal is enhanced[71,72]. Ren et al. constructed a graphene oxide-photonic crystal coupled bilayer sensor to distinguish biogenic amines and pharmaceutical amines with similar structures[73]. Based on electrostatic and π-π stacking interactions, fluorescence resonance energy transfer (fret) occurs between the fluorescent molecule and GO, resulting in fluorescence quenching of the fluorescent molecule. Based on the competitive adsorption behavior of amine and fluorescent molecules to GO, when the sensor contacts the amine molecule, the fluorescent molecule is desorbed and permeates into the photonic crystal. When the emission wavelength of the fluorescent molecule overlaps with the blue edge of the photonic band gap, the slow light effect of the photonic crystal significantly enhances the fluorescence intensity. They effectively distinguished ten biogenic amines and seven pharmaceutical amines based on the differences in the characteristic fluorescence signals of amine molecules.
The development of clinical diagnostic technology requires Point-of-care testing (POCT) devices with high sensitivity and multiplexing[74]. Liu Hong et al. self-assembled SiO2 and poly (methyl methacrylate-butyl acrylate) (P (MMA-BA)) nanoparticles on a polydimethylsiloxane (PDMS) microcavity mold, then infiltrated and etched the SiO2 with nitrocellulose, and finally peeled off the mold to successfully construct a flexible photonic crystal biochemical sensor (MSP)[74]. Subsequently, they dropped fluorescein isothiocyanate (FITC) on MSP and glass substrates respectively to explore the fluorescence enhancement effect of photonic crystal structure on FITC. It was found that the fluorescence intensity of FITC on MSP was higher than that of the control group. The enhancement of fluorescence intensity can be attributed to two aspects: on the one hand, the higher porosity of the inverse opal photonic crystal increases the possibility of collision between fluorescent molecules; On the other hand, the slow light effect of photonic crystals significantly increases the effective optical path and enhances the fluorescence intensity.
Using the same method, they also prepared a novel microfluidic device (EC MSP) with 8 channels (fig. 7) to detect three cancer markers, carcinoembryonic antigen (CEA), alpha-fetoprotein (AFP) and carbohydrate antigen 125 (CA125), by luminol-p-iodophenol -H2O2 chemiluminescence[74]. The fluorescence intensity of the three cancer markers was linearly correlated with the concentration, and the detection limit was as low as ng.
Photonic crystal is a kind of nanomaterial which changes periodically in space. It is an effective way to adjust the local electromagnetic field. The combination of surface plasmon polaritons and photonic crystal can increase the fluorescence intensity more effectively[75]. Song Hongwei et al. Coated Ag-Au nanoparticles on polymethyl methacrylate (PMMA) photonic crystal with opal structure, and successfully constructed a 3D photonic crystal biochemical sensor with Ag-Au-carbon dot-PMMA composite structure for high-resolution fingerprint identification[75]. The interaction between the incident light and the free electrons on the surface of the metal nanoparticles leads to the local surface plasmon resonance (LSPR), which leads to the increase of the fluorescence intensity. The synergistic effect of photonic crystal and LSPR can not only modulate the position of the photonic band gap, but also significantly enhance the fluorescence intensity and quantum efficiency of the photonic crystal. The fluorescence enhanced photonic crystal biochemical sensor for detecting biochemical molecules is shown in Table 2.

4.3 Raman enhance photonic crystal biochemical sensor

There are two main theories to explain the effect of surface-enhanced Raman scattering (SERS). One is the electromagnetic resonance theory, that is, LSPR enhances Raman scattering[5]. The enhancement of the LSPR effect can be obtained when the photonic band gap of the photonic crystal is close to the maximum absorption wavelength of the metal nanoparticles[25]. Zhao Xiangwei et al. Synthesized Au nanoparticles in situ in inverse opal photonic crystal capillary column for SERS analysis[78]. The inverse opal photonic crystal with a high specific surface area enhances the optical field near the "hot spot" Au nanoparticle and enhances the Raman scattering signal of the analyte. The sensor can be used to detect creatinine in artificial urine samples with a detection limit as low as 0.9 mg/dL. Chen Xudong et al. Deposited Ag on SiO2 photonic crystals by magnetron sputtering to construct PCs-Ag sensors with significantly enhanced Raman scattering effect. The detection limit of adenine is as low as nmol/L, which clarifies the development path for its application in biomedical diagnosis[79]. Similarly, Lee et al. achieved detection of rhodamine 6G (R6G) with detection limits down to the pmol/L level by alternately sputtering Ag and amorphous silicon onto photonic crystals (Fig. 8)[80].
The other is the chemical theory that the enhancement of Raman scattering depends on the change of Raman scattering cross section[5]. Effective light-mass coupling plays a decisive role in SERS detection[81]. Li et al. Constructed a AgClxBr1-x nanocubic photonic crystal and coated the surface of the photonic crystal with thiophenol to prevent photoexcitation from causing the reduction of AgClxBr1-x nanoparticles[49]. The results show that SERS is mainly caused by the Herzberg-Teller vibration coupling between the AgClxBr1-x nanocubic photonic crystal and thiophenol molecule and the photonic band gap of the photonic crystal.
Specificity and reproducibility have been major challenges in SERS applications. Wang Mengfan et al. Immobilized "hot spot" Au nanoparticles uniformly on the reverse opal photonic crystal molecularly imprinted polymer, and constructed a sandwich Raman-enhanced photonic crystal molecularly imprinted biochemical sensor[21]. The Raman spectrum shows that the 778 cm-1 is the characteristic peak of R6G, and the sensor can well distinguish R6G from other structural analogues. The detection range of the sensor is 10-10~10-4mol/L, the relative deviation is 8. 92% after 8 cycles, and the sensor has good stability.

4.4 Biochemical sensor base on evanescent wave enhanced photonic crystal

Evanescent Wave refers to the phenomenon of total reflection of light waves between two media. Its amplitude decays exponentially with the direction away from the interface. Van Leest et al. First proposed to capture a single bacterium using the properties of a locally enhanced evanescent wave in a photonic crystal cavity (Fig. 9)[82]. They first fabricated a photonic crystal cavity embedded in planar silicon, and then combined the photonic crystal with microfluidics technology to precisely control the light intensity needed for single cell research. Bacteria were carried to the cavity by a 5 μm/s microcurrent, and when they reached the evanescent field of the photonic crystal cavity, they were trapped in the cavity. When the light source of the cavity is turned off, the bacteria are released instantaneously. This study proves that under the condition of maintaining light supply, bacteria can be captured for a long time (> 5 min), which is of great significance in disease diagnosis and pollution prevention.

4.5 Urface infrared absorption enhanced photonic crystal biochemical sensor

Surface-enhanced infrared absorption spectroscopy (SEIRA) has high sensitivity, but its practical application is limited by its high dissipation loss and low optical quality[83]. In order to overcome the above shortcomings, Chang et al. spin-coated polyethyleneimine (PEI), which has selective recognition ability for CO2, on the surface of photonic crystal, realized the increase of effective path and the enhancement of electric field intensity, and constructed a surface-enhanced infrared absorption CO2 sensor with low detection limit (20 ppm) and fast detection ability (2 min)[83].

4.6 Photoelectric signal enhanced photonic crystal biochemical sensor

In recent years, with the increasing research of photoelectric sensors, photonic crystals as electrode modification materials have also received extensive attention. The porous structure of inverse opal photonic crystals promotes the transfer of matter and the migration of charge, and shows excellent photoelectric properties[41,84]. In addition, the photonic band gap can increase the effective path length of light, which is conducive to the interaction of light and mass[85]. Song Hongwei et al. used oleic acid-coated CsPbBr1.5I1.5 quantum dots (QDs) as Photoelectrochemical active substances, fixed them on the porous framework of TiO2 inverse opal photonic crystals (IOPCs), and coated them with Nafion film to protect the CsPbBr1.5I1.5QDs, so as to construct a photoelectric signal enhanced photonic crystal biochemical sensor with high stability, good sensitivity, excellent selectivity and instant response for dopamine detection (Figure 10)[85]. The edge of the conduction band of the CsPbBr1.5I1.5QDs is slightly higher than the TiO2, so that the electrons of the CsPbBr1.5I1.5QDs can be transmitted to the conductive glass through the TiO2 by using a 500 W xenon lamp to generate an obvious electric signal, thereby effectively inhibiting the electron recombination of the CsPbBr1.5I1.5QDs; The coating of Nafion membrane makes it possible for CsPbBr1.5I1.5QDs to exist in water for a long time, which overcomes the shortcomings of its biological application. The high specific surface area of the TiO2 inverse opal photonic crystal provides multiple active sites for the self-assembly growth of the CsPbBr1.5I1.5QDs and effectively enhances the photocurrent response; Moreover, the energy level of dopamine is higher than the valence band of the CsPbBr1.5I1.5QDs, which makes the detection of dopamine possible. Under the excitation of 600 nm light, the concentration of dopamine was positively correlated with the intensity of the photocurrent signal, and the detection limit was as low as 0. 012 μmol/L. The development of the sensor opens up a new prospect for the research of photoelectric enhanced photonic crystal biochemical sensors based on perovskite quantum dots, and has inestimable value for biomedical clinical detection.
Choosing semiconductor materials with appropriate band gap to construct heterojunction is helpful to promote charge separation, and the introduction of inverse opal photonic crystal is an effective method to enhance the Photoelectrochemical performance[86]. Therefore, based on the triple heterostructure of PPy/gC3N4/WO3 inverse opal photonic crystal, Zhao Huimin et al. Built a photonic crystal biochemical sensor with effective separation of photogenerated electron-hole pairs and strong optical adsorption[86]. The biosensor showed high sensitivity and specificity for the detection of oxytetracycline (OTC) in the range of 0. 01-5 nmol/L with a detection limit of 0. 004 nmol/L. The combination of multiple heterojunctions and inverse opal photonic crystals can further broaden the application of new semiconductor materials in the field of biochemical analysis and separation.

4.7 Other photonic crystal biochemical sensor

In addition to the above typical photonic crystal biochemical sensors, photonic crystal biochemical sensors based on molecular imprinting specific recognition have also received a lot of attention. Pan Daodong et al achieved the goal of selective extraction of S-layer protein (SLP) from complex Lactobacillus acidophilus CICC 6074 by constructing molecularly imprinted photonic crystal membrane (MIPP)[87]. The inverse opal photonic crystal has large pores, which is beneficial to the rapid passage of template molecules, and is particularly suitable for the detection of biological macromolecules, and has the advantage of rapid response. After MIPP specifically binds to or elutes SLP, the volume of the photonic crystal microcavity changes, resulting in a shift of the Bragg diffraction peak. In addition, the linear detection range of MIPP is between 0 and 1 mg/mL, the detection limit is as low as 1 ng/mL, and the anti-interference ability is excellent, which makes the label-free quantitative detection of SLP in complex matrices possible. Levodropropizine (LDPZ) was used as a template molecule for the first time to construct LDPZ molecularly imprinted inverse opal photonic crystal films, which expanded the application of molecular imprinting in the detection of basic compounds[88]. Other photonic crystal biochemical sensors that detect biochemical molecules are detailed in Table 3.
In addition, the introduction of photonic crystals into semiconductors has been shown to be an effective way to enhance the photocatalytic activity of semiconductors[94]. Ge Jianping et al. Developed a photonic crystal supported CdS quantum dots (QDs) photocatalyst[94]. When the photonic band gap of the photonic crystal is matched with the absorption edge of the CdS QDs, the photocatalytic activity of the photonic crystal supported CdS QDs is 6.4 to 8.8 times higher than that of a non-photonic crystal supported CdS QD during hydrogen evolution. Photonic crystal (PC) -supported quantum dots (QDs) have excellent electrical conductivity and visible light absorption ability, which show great potential in the application of photocatalytic materials.

5 Conclusion and prospect

In this paper, the latest research progress of photonic crystal biochemical sensors is reviewed from the point of view of the interaction effect between photonic crystal and light. Visible photonic crystal biochemical sensor has the advantage of being intuitive and visible, and has wide application value in the field of biochemical analysis and sensing; Enhanced photonic crystal biochemical sensors are mainly based on the periodic spatial structure of photonic crystals, which have the ability of signal amplification and have broad development prospects in the fields of food safety, biomedicine, clinical diagnosis and environmental pollution.
In general, photonic crystal biosensors are still in the initial stage, although a large number of research articles on photonic crystal biosensors have been reported, their construction is limited to the laboratory stage, and there are some problems to be solved: (1) low biocompatibility of photonic crystal biochemical sensors; (2) that mechanical property of the photonic crystal biochemical sensor is poor, and the reusability is limit; (3) The preparation of photonic crystals, which is closely related to visual detection, is still unsatisfactory, and how to produce highly uniform photonic crystals on a large scale and controllably needs further study.
The introduction of the ionic liquid or the deep eutectic solvent is beneficial to increasing the biocompatibility of the photonic crystal biochemical sensor[23][95]; The introduction of the sacrificial bond can shorten the healing time and improve the self-healing efficiency of the photonic crystal biochemical sensor[96,97][97]. With the continuous development of science and technology, it can be expected that photonic crystal biochemical sensors will play an important role in food safety, biomedicine, environmental monitoring, pollution control and clinical diagnosis.

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