Two-photon polymerization lithography for imaging optics

Optical imaging systems have greatly extended human visual capabilities,enabling the observation and understanding of diverse phenomena.Imaging technologies span a broad spectrum of wavelengths from x-ray to radio frequencies and impact research activities and our daily lives.Traditional glass lenses are fabricated through a series of complex processes,while polymers offer versatility and ease of production.However,modern applications often require complex lens assemblies,driving the need for miniaturization and advanced designs with micro-and nanoscale features to surpass the capabilities of traditional fabrication methods.Three-dimensional(3D)printing,or additive manufacturing,presents a solution to these challenges with benefits of rapid prototyping,customized geometries,and efficient production,particularly suited for miniaturized optical imaging devices.Various 3D printing methods have demonstrated advantages over traditional counterparts,yet challenges remain in achieving nanoscale resolutions.Two-photon polymerization lithography(TPL),a nanoscale 3D printing technique,enables the fabrication of intricate structures beyond the optical diffraction limit via the nonlinear process of two-photon absorption within liquid resin.It offers unprecedented abilities,e.g.alignment-free fabrication,micro-and nanoscale capabilities,and rapid prototyping of almost arbitrary complex 3D nanostructures.In this review,we emphasize the importance of the criteria for optical performance evaluation of imaging devices,discuss material properties relevant to TPL,fabrication techniques,and highlight the application of TPL in optical imaging.As the first panoramic review on this topic,it will equip researchers with foundational knowledge and recent advancements of TPL for imaging optics,promoting a deeper understanding of the field.By leveraging on its high-resolution capability,extensive material range,and true 3D processing,alongside advances in materials,fabrication,and design,we envisage disruptive solutions to current challenges and a promising incorporation of TPL in future optical imaging applications.

Two-Photon Fluorescence Properties and Ultrafast Responses of a Hyperbranched Diketo-Pyrrolo-Pyrrole Polymer with Triphenylamine as the Core

The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne （hb-DPP-J2） with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are studied. The polymer has a D-π-A-π-D conjugated structure along the extended polyyne w-bridge systems, and the effective condugated unit repeats itself in the whole hyperbranehed polymer chain. The polymer exhibits a large two-photon absorption cross section and high fluorescence quantum yields. The ultrafast dynamic results give a deep understanding of the excited energy transfer processes under excitation, and reveal a long relaxation lifetime of the intramolecular charge transfer （ICT） state.

Ultracompact phase plate fabricated by femtosecond laser two-photon polymerization for generation of Mathieu–Gauss beams

The Mathieu beam is a typical nondiffracting beam characterized by its propagation invariance and self-reconstruction.These extraordinary properties have given rise to potentialities for applications such as optical communications,optical trapping,and material processing.However,the experimental generation of Mathieu–Gauss beams possessing high quality and compactness is still challenging.In this work,even and helical Mathieu phase plates with different orders m and ellipticity parameters q are fabricated by femtosecond laser two-photon polymerization.The experimentally generated nondiffracting beams are propagationinvariant in several hundred millimeters,which agree with numerical simulations.This work may promote the miniaturization of the application of nondiffracting beams in micronanooptics.

High-aspect 3D two-photon polymerization structuring with widened objective working range (WOW-2PP)

We developed a novel two-photon polymerization(2PP)configuration for fabrication of high-aspect three-dimensional(3D)structures,with an overall height larger than working distance of the microscope objective used for laser beam focusing into a photosensitive material.This method is based on a modified optical 2PP setup,where a microscope objective(1003 high N.A.),immersion oil and cover glass can be moved together into the photosensitive material,resulting in an effective higher and wider objective working range(WOW-2PP).The proposed technique enables the fabrication of high-aspect structures with sub-micrometer process resolution.3D structures with a height of 7 mm are demonstrated,which could hardly be built with the conventional 2PP set-up due to refractive index mismatch and laser beam disturbances.

Simultaneous additive and subtractive three-dimensional nanofabrication using integrated two-photon polymerization and multiphoton ablation

Modern three-dimensional nanofabrication requires both additive and subtractive processes.However,both processes are largely isolated and generally regarded as incompatible with each other.In this study,we developed simultaneous additive and subtractive fabrication processes using two-photon polymerization followed by femtosecond(fs)laser multiphoton ablation.To demonstrate the new capability,submicrometer polymer fibers containing periodic holes of 500-nm diameter and microfluidic channels of 1-mm diameter were successfully fabricated.This method combining both two-photon polymerization and fs laser ablation improves the nanofabrication efficiency and enables the fabrication of complex three-dimensional micro-/nanostructures,promising for a wide range of applications in integrated optics,microfluidics and microelectromechanical systems.

Isotropic sintering shrinkage of 3D glass-ceramic nanolattices:backbone preforming and mechanical enhancement

There is a perpetual pursuit for free-form glasses and ceramics featuring outstanding mechanical properties as well as chemical and thermal resistance.It is a promising idea to shape inorganic materials in three-dimensional(3D)forms to reduce their weight while maintaining high mechanical properties.A popular strategy for the preparation of 3D inorganic materials is to mold the organic–inorganic hybrid photoresists into 3D micro-and nano-structures and remove the organic components by subsequent sintering.However,due to the discrete arrangement of inorganic components in the organic-inorganic hybrid photoresists,it remains a huge challenge to attain isotropic shrinkage during sintering.Herein,we demonstrate the isotropic sintering shrinkage by forming the consecutive–Si–O–Si–O–Zr–O–inorganic backbone in photoresists and fabricating 3D glass–ceramic nanolattices with enhanced mechanical properties.The femtosecond(fs)laser is used in two-photon polymerization(TPP)to fabricate 3D green body structures.After subsequent sintering at 1000℃,high-quality 3D glass–ceramic microstructures can be obtained with perfectly intact and smooth morphology.In-suit compression experiments and finite-element simulations reveal that octahedral-truss(oct-truss)lattices possess remarkable adeptness in bearing stress concentration and maintain the structural integrity to resist rod bending,indicating that this structure is a candidate for preparing lightweight and high stiffness glass–ceramic nanolattices.3D printing of such glasses and ceramics has significant implications in a number of industrial applications,including metamaterials,microelectromechanical systems,photonic crystals,and damage-tolerant lightweight materials.

Two-photon polymerization of femtosecond high-order Bessel beams with aberration correction

In the femtosecond two-photon polymerization(2PP)experimental system,optical aberrations degrade the fabrication quality.To solve this issue,a multichannel interferometric wavefront sensing technique is adopted in the adaptive laser processing system with a single phase-only spatial light modulator.2PP fabrications using corrected high-order Bessel beams with the above solution have been conducted,and high-quality microstructure arrays of microtubes with 20μm diameter have been rapidly manufactured.The effectiveness of the proposed scheme is demonstrated by comparing the beam intensity distributions and 2PP results before and after aberration corrections.

A new series of two-photon polymerization initiators:Synthesis and nonlinear optical properties

Four photopolymerization initiators with D-π-D (D,donor; π,conjugation system) structure have been synthesized by solvent-free reaction and characterized by 1H NMR spectroscopy,IR and elemental analysis. The one-photon and two-photon excited fluorescence have been investigated in different solvents. Experimental results of the one-photon and two-photon absorption cross sections show different trends in OPA and TPA ability with different substitution groups in donor units.

Synthesis of two carbazole-based dyes and application of two-photon initiating polymerization

Two carbazole-based polymerization initiators possessing blue fluorescence emission have been synthesized via Wittig reaction in the solid phase at room temperature.Two-photon excited fluorescence(TPEF) spectra for them were investigated under 800 nm fs laser pulse and two-photon absorption cross sections were determined by the Z-scan technique.Then two-photon initiating polymerization(TPIP) microfabrication experiments were successfully carried out.Three-dimensional lattice and artificial defects were gained,indicating that they were viable candidates for the two-photon polymerization initiator in practical application of microfabrication.

3D printed fiber-optic nanomechanical bioprobe

Ultrasensitive nanomechanical instruments,e.g.atomic force microscopy(AFM),can be used to perform delicate biomechanical measurements and reveal the complex mechanical environment of biological processes.However,these instruments are limited because of their size and complex feedback system.In this study,we demonstrate a miniature fiber optical nanomechanical probe(FONP)that can be used to detect the mechanical properties of single cells and in vivo tissue measurements.A FONP that can operate in air and in liquids was developed by programming a microcantilever probe on the end face of a single-mode fiber using femtosecond laser two-photon polymerization nanolithography.To realize stiffness matching of the FONP and sample,a strategy of customizing the microcantilever’s spring constant according to the sample was proposed based on structure-correlated mechanics.As a proof-of concept,three FONPs with spring constants varying from 0.421 N m^(−1)to 52.6 N m^(−1)by more than two orders of magnitude were prepared.The highest microforce sensitivity was 54.5 nmμN^(−1)and the detection limit was 2.1 nN.The Young’s modulus of heterogeneous soft materials,such as polydimethylsiloxane,muscle tissue of living mice,onion cells,and MCF-7 cells,were successfully measured,which validating the broad applicability of this method.Our strategy provides a universal protocol for directly programming fiber-optic AFMs.Moreover,this method has no special requirements for the size and shape of living biological samples,which is infeasible when using commercial AFMs.FONP has made substantial progress in realizing basic biological discoveries,which may create new biomedical applications that cannot be realized by current AFMs.

Femtosecond laser fabrication of 3D templates for mass production of artificial compound eyes

Compound eyes are unique optical imaging systems that consist of numerous separate light-sensitive units(ommatidia).Attempts have been made to produce artificial compound eyes via advanced 3 D nanotechnologies.Among them,femtosecond laser direct writing(FsLDW)technology has emerged as an effective strategy due to its distinct advantages in 3 D designable and high precision fabrication capability.However,the point-by-point scanning process results in a very low fabrication efficiency,limiting the practical applications of the FsLDW technology.To solve this problem,we propose a high-efficiency method for the mass production of 3 D artificial compound eyes using a photopolymer template fabricated by FsLDW.The resultant 3 D SU-8 compound eye templates could be used to replicate polydimethylsiloxane(PDMS)compound eyes many times(over 50 times)with a highly improved efficiency(nearly 20 times higher than the efficiency of direct fabrication using the point-by-point FsLDW).The PDMS replicas showed good focusing and imaging performances.We anticipate that this method may serve as an enabler for the mass production of 3 D artificial compound eyes and promote their practical applications in the near future.

Enhancement of two-photon absorption cross section and singlet-oxygen generation in porphyrin-cored star polymers

We report a newly synthesized polymer of a star-shaped porphyrin compound(TPA-FxP) with four oligofluorene arms at its meso positions with the pronounced enhancement of the two-photon properties and the generation of singlet oxygen by utilizing the two-photon excited fluorescence resonance energy transfer.The steady-state spectra and transient triplet-triplet absorption spectra give evidence that the enhanced two-photon absorption cross section results from not only the through-space energy transfer(Frster) but also the through-bond energy transfer between conjugated peripheral oligofluorene arms and the porphyrin core.The two-photon absorption cross section at 780 nm up to 3360 GM(1 GM = 10-50 cm4·s/photon) of TPA-FxP was obtained,which is comparable to the highest values reported from other similar chemically modified porphyrin core compounds.Furthermore,the enhanced production of singlet oxygen under two-photon absorption conditions is also reported.

Femtosecond-laser direct writing 3D micro/nano-lithography using VIS-light oscillator

Here we report a femtosecond laser direct writing(a precise 3D printing also known as two-photon polymerization lithography) of hybrid organic-inorganic SZ2080^(TM)pre-polymer without using any photo-initiator and applying ~100 fs oscillator operating at 517 nm wavelength and 76 MHz repetition rate. The proof of concept was experimentally demonstrated and benchmarking 3D woodpile nanostructures, micro-scaffolds, free-form micro-object “Benchy” and bulk micro-cubes are successfully produced. The essential novelty underlies the fact that non-amplified laser systems delivering just 40-500 p J individual pulses are sufficient for inducing localized cross-linking reactions within hundreds of nanometers in cross sections. And it is opposed to the prejudice that higher pulse energies and lower repetition rates of amplified lasers are necessary for structuring non-photosensitized polymers. The experimental work is of high importance for fundamental understanding of laser enabled nanoscale 3D additive manufacturing and widens technology’ s field of applications where the avoidance of photo-initiator is preferable or is even a necessity, such as micro-optics, nano-photonics, and biomedicine.

Surface-state triggered solvatochromism of carbonized polymer dot and its two-photon luminescence

This study reports a new nitrogen-doped carbonized polymer dot(CPD)-based solvatochromic probe.Its color-changing for different solvents was explored in detail by the measurements of photophysical parameters(involving Stokes shifts,fluorescence quantum yield,fluorescence lifetime,radiative decay rate constant,and non-radiative decay rate constant)and the following analyses according to Lippert–Mataga equation and Kamlet–Taft model.The hydrogen bonding effect of the CPD in protonic solvents was semi-quantitatively assessed.It takes charge of the solvatochromic phenomenon,especially in proton solvents.Interestingly,this CPD exhibits two-photon solvatochromism.Moreover,the relations between the photophysical parameters and the surface states of CPD in aprotic and proton solvents were depicted.The results reveal the nitrogen doping in the CPD impacts the up-and down-conversion solvatochromic features from the comparison between N-free and N-doped CPDs in many characterizations.In addition,this N-doped CPD was dispersed into polymer matrices to fabricate tunable solid-state luminescent films,which is another model for evidencing the interactions of the CPD with surroundings.This study is of significance in understanding the surface-state controlled luminescence in the CPDs,and will be beneficial for developing new smart,responsive carbon-based nanoprobes.

3D printed fiber sockets for plug and play micro-optics

Integrating micro-optical components at the end facet of an optical fiber enables compact optics to shape the output beam(e.g.collimating,focusing,and coupling to free space elements or photonic integrated circuits).However,the scalability of this approach is a longstanding challenge as these components must be aligned onto individual fiber facets.In this paper,we propose a socket that enables easy slotting of fibers,self-alignment,and coupling onto micro-optical components.This integrated socket can be detached from the substrate upon fiber insertion to create a stand-alone optical system.Fabrication is done using nanoscale 3D printing via two-photon polymerization lithography onto glass substrates,which allows multiple sockets to be patterned in a single print.We investigated variations in socket design and evaluated the performance of optical elements for telecom wavelengths.We obtained an alignment accuracy of∼3.5μm.These socket designs can be customized for high efficiency chip to fiber coupling and extended to other spectral ranges for free-form optics.

PHOTOSWITCHABLE NANOFLUOROPHORES FOR INNOVATIVE BIOIMAGING

Photosensitive fluorescent probes have become powerful tools in chemical biology and molecular biophysics,which are used to investigate cellular processes with high temporal and spatial resolution.Accordingly,photosensitive fluorescent probes,including photoactivatable,photoconvertible,and photoswitchable fluorophores,have been extensively developed during the past decade.The photoswitchable fluorophores have received much attention because they highlight cellular events clearly.This minireview summarizes recent advances of using reversibly photoswitchable fluorophores and their applications in innovative bioimaging.Photoswitchable fluorophores include photoswitchable fluorescent proteins,photoswitchable fluorescent organic molecules(dyes),and photoswitchable fluorescent nanoparticles.Several strategies have been developed to synthesize photoswitchable fluorophores,including engineering combination proteins,chemical synthesis,polymerization,and self-assembly.Here we concentrate on polymer nanoparticles with optically switchable emission properties:either fluorescence on/offor dualalternating-color fluorescence photoswitching.The essential mechanisms of fluorescence photoswitching enable different types of photoswitchable fluorophores to change emission intensity or wavelength(color)and thus validating the basis of the fluorescence on/offor dual-color photoswitching design.Generally the possible applications of any fluorophores are to label biological targets,followed by specific imaging.The newly developed photoswitchable fluorophores enable super-resolution fluorescence imaging because of their photosensitive emission.Finally,we summarize the important area regarding future research and development on photoswitchable fluorescent nanoparticles.

Polymeric dual-modal imaging nanoprobe with two-photon aggregation-induced emission for fluorescence imaging and gadolinium-chelation for magnetic resonance imaging

Nanoprobes that offer both fluorescence imaging(FI)and magnetic resonance imaging(MRI)can provide supplementary information and hold synergistic advantages.However,synthesis of such dual-modality imaging probes that simultaneously exhibit tunability of functional groups,high stability,great biocompatibility and desired dual-modality imaging results remains challenging.In this study,we used an amphiphilic block polymer from(ethylene glycol)methyl ether methacrylate(OEGMA)and N-(2-hydroxypropyl)methacrylamide(HPMA)derivatives as a carrier to conjugate a MR contrast agent,Gd-DOTA,and a two-photon fluorophore with an aggregation-induced emission(AIE)effect,TPBP,to construct a MR/two-photon fluorescence dual-modality contrast agent,Gd-DOTA-TPBP.Incorporation of gadolinium in the hydrophilic chain segment of the OEGMA-based carrier resulted in a high r_(1)value for Gd-DOTA-TPBP,revealing a great MR imaging resolution.The contrast agent specifically accumulated in the tumor region,allowing a long enhancement duration for vascular and tumor contrast-enhanced MR imaging.Meanwhile,coupling TPBP with AIE properties to the hydrophobic chain segment of the carrier not only improved its water solubility and reduced its cytotoxicity,but also significantly enhanced its imaging performance in an aqueous phase.Gd-DOTA-TPBP was also demonstrated to act as an excellent fluorescence probe for two-photon-excited bioimaging with higher resolution and greater sensitivity than MRI.Since high-resolution,complementary MRI/FI dual-modal images were acquired at both cellular and tissue levels in tumor-bearing mice after application of Gd-DOTA-TPBP,it has great potential in the early phase of disease diagnosis.

二维和三维微/纳高效精密加工中的纳立体刻印工艺(英文)

双光子聚合(TPP)是通过光敏剂中的非线性双光子吸收过程所引发的,其作为一种新工艺,自问世以来,已在二雏和三维加工聚合应用领域中得到广泛研究．对于二维纳米图案的加工,纳复制工艺已经演变为体素模板扫描方法．该方法用黑白双色2块图作为设计图案,并转排成体素模板以控制聚焦激光素的开关．复杂的三维微结构也可以采用多重断面分层叠加的方法进行加工,各断面的扫描数据从三维CAD数据中得到．在聚合反应后,没有固化的液态树脂,其采用在树脂上浇注类似于酒精之类溶剂的方法去除,从而显露出聚合的微结构．在前期的工作中,已经成功地加工出了高空间分辨力的三维微光学器件,分辨力约为100nm．微机械器件和光子晶体等的近期研究工作提高了其TPP的效率和精度．介绍了近来开发的基于TPP的一些微加工工艺．

NIR Emission Nanoparticles Based on FRET Composed of AIE Luminogens and NIR Dyes for Two-photon Fluorescence Imaging

Near-infrared(NIR) nanoparticles(NPs) based on fluorescence resonance energy transfer(FRET) were prepared by coencapsulation of a red aggregation-induced emission(AIE) molecule, 2-(4-bromophenyl)-3-(4-(4-(diphenylamino)styryl)phenyl)fumaronitrile(TB), and a commercial NIR fluorescence dye, silicon 2,3-naphthalocyanine bis(trihexylsilyloxide)(NIR775) with an amphiphilic polymer poly(styrene-co-maleic anhydride)(PSMA). The surface of the NPs, PSMA@TB/NIR775, was modified with poly(ethylene glycol)(PEG) to increase the in vivo biocompatibility of the NPs. The PSMA@TB/NIR775 NPs showed a strong NIR(780 nm) narrow emission and excellent two-photon absorption property. Moreover, the NPs exhibited good monodispersity, stability, and low cytotoxicity.Under the excitation of a 1040 nm femtosecond(fs) laser, the emission peaks at 680 nm of TB and 780 nm of NIR775 excited by FRET were obtained. We utilized PSMA@TB/NIR775 NPs as fluorescent contrast agents for two-photon excited NIR microscopic imaging, and good NIR imaging effect of mouse brain vasculature was obtained with the imaging depth of about 150 μm. The FRET strategy by coencapsulating AIE molecule and NIR dye will be helpful in preparing more narrow emission NIR probes for deep-tissue biological imaging.

Two-photon AIE probe conjugated theranostic nanoparticles for tumor bioimaging and pH-sensitive drug delivery

Nanoparticles armed with chemotherapy drug and fluorescence probe have become an effective anticancer strategy for their advantages in cancer diagnosis and treatment.However,fluorophore for diagnostic medicine with deep penetration depth and high resolution are still very rare,while rational designs are also required to improve the tumor retention and target-site drug delivery.Herein,a two-photon fluorophore with aggregation-induced emission and large two-photon absorption cross-section has been designed for two-photon bioimaging,and a novel theranostic nanoplatform is also constructed based on doxorubicin and the two-photon fluorophore conjugated copolymer,P(TPMA-co-AEMA)-PEI(DA)-Blink-PEG (PAEEBlink-DA).The micelles maintain a “stealth” property during blood circulation and is activated in the acidic tumor microenvironment,which triggers the charge-conversion and results in enhanced micellar internalization.Meanwhile,PAEMA chains can convert from hydrophobicity to hydrophilicity with accelerated drug release and particle size expansion.The enlarged particle size would potentially extend the retention time of these micelles.Moreover,a great AIE active two-photon bioimaging with tissue penetration depth up to 150 μm is observed and the in vivo biodistribution of nanoparticles can be traced.The in vivo antitumor results further indicate the obvious reduction of adverse effect and enhanced treatment effect of these micelles,proving that these PAEEBlink-DA micelles would be a potential candidate for tumor theranostic applications.